CN113321683B - Compounds containing P-N bonds and preparation method thereof - Google Patents
Compounds containing P-N bonds and preparation method thereof Download PDFInfo
- Publication number
- CN113321683B CN113321683B CN202110631151.7A CN202110631151A CN113321683B CN 113321683 B CN113321683 B CN 113321683B CN 202110631151 A CN202110631151 A CN 202110631151A CN 113321683 B CN113321683 B CN 113321683B
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- cdcl
- nmr
- phosphine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5463—Compounds of the type "quasi-phosphonium", e.g. (C)a-P-(Y)b wherein a+b=4, b>=1 and Y=heteroatom, generally N or O
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5355—Phosphoranes containing the structure P=N-
Abstract
The invention belongs to the field of compound intermediate synthesis, and particularly relates to a method for preparing a compound containing a P-N bond and a prepared P-N compound. The synthesis method comprises the following steps: phosphine-containing compounds and 3-substituted-1, 4, 2-dioxazole-5-ketone are used as raw materials and react under the condition of an iron catalyst to generate compounds of formulas I to V containing P-N bonds, and specifically comprise amido phosphine, imido phosphonamide, phosphonamide and amido phosphine compounds. The invention utilizes secondary phosphine and 3-substituted-1, 4, 2-dioxazole-5-ketone as reaction reagents, the substrates are simple and easy to obtain, the catalyst is cheap halogenated iron, various P-N bond compounds can be synthesized by regulating and controlling different reaction conditions, and a brand new synthesis strategy is provided for the synthesis of phosphorus/nitrogen ligands. The method avoids the use of potentially hazardous azides or toxic phosphine halides, and has potential synthetic applications.
Description
Technical Field
The invention belongs to the technical field of chemical intermediates, and relates to a compound containing a P-N bond and a preparation method thereof.
Background
The P-N bond widely exists in natural drug molecules, is also widely applied to the design and synthesis of ligands and is commonly used in the field of asymmetric catalysis. Conventional P-N bonding is largely limited to the Staudinger reaction or nucleophilic substitution of phosphine halide compounds by amine nucleophiles. Although the staudinger reaction is widely used, the azide used in the staudinger reaction has potential explosiveness, and the mass synthesis has certain limitations. Although the nucleophilic substitution method of the amine nucleophile on the phosphine halide compound is simple, the application of the phosphine halide compound is also limited by the high toxicity of the amine nucleophile, so that the development of a milder method for synthesizing the compound containing the P-N bond has important significance.
Dioxazolone is a common amination reagent (ACS Catal.2020,10,4751) and a green and safe acylnitrene precursor, as early as 1951, a substrate of dioxazolone was first synthesized by Beck project group (chem. Ber.1951,84,688), in 1968, and Sauer and Mayer project groups found that under heating or illumination conditions, dioxazolone can remove carbon dioxide to perform amination reaction with thioether or sulfoxide respectively (Tetrahedron Lett.1968,9,319). Since this dioxazolone has not been studied further, until 2014, after the Bolm group applied a transition metal Ru catalyst to the amination reaction of a thioether or sulfoxide with dioxazolone, dioxazolone has not gained much attention. After the dioxazole ketone forms metal nitrene, various types of amination can be realized, a series of X-N bonds are constructed, such as amination of thioether or sulfoxide (ACIE,2014,53,5639), C-H bond amination (Science,2018,359,1016), N-H bond amination (Nature chem.2021,13,378) and the like, and the method is a very mild and efficient amination strategy. The acyl azide compound can also be used as an acyl nitrene precursor, but the preparation and the storage of the acyl azide compound are harsh and have certain dangerousness, the acyl azide compound is easy to decompose nitrogen to be damaged, and compared with the acyl azide compound, the dioxazolone is safe and stable, the preparation is convenient, and the acyl azide compound is widely used at present. The metal nitrene intermediate generally has stronger electrophilicity, and the development of a novel nucleophilic reagent for capturing the metal nitrene intermediate can widen the application range of the dioxazolone.
The metals used in the transition metal catalyzed nitrene transition reaction are mostly noble metals, such as Ir, Ru, Rh, Co and the like. The iron catalyst capable of replacing noble metals is an ideal catalyst, has the characteristics of environmental friendliness, low toxicity, easiness in degradation, low residue, low price, easiness in obtaining and the like, has wide application in nitrene chemistry, has more potential for industrial application compared with the noble metals in the nitrene transfer reaction catalyzed by iron, and promotes the research process of the nitrene transfer reaction to a great extent.
Compounds containing P-N bonds are often used extensively as ligands. For example, phosphorus atoms in amido phosphine and amido phosphine have stronger coordination property and are applied to ligand design, and nitrogen in phosphonamide can also be used as a ligand to participate in metal catalytic reaction; the imido phosphonamide can form a unique four-membered ring metal complex with metal to participate in catalytic reaction. The development of a simple and feasible synthesis method starting from easily obtained substrates has high application value in the efficient synthesis of the compounds.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a compound containing a P-N bond and a preparation method thereof. The synthesis strategy of the invention is to utilize secondary/tertiary phosphine as a nucleophilic reagent to react with electrophilic metal nitrene so as to construct P-N bond, and to synthesize diversified P-N bond compounds by changing different reaction conditions, and the strategy is simple and effective, and synthesizes diversified P-N compounds, including amido phosphine, imido phosphamide, phosphamide and amido phosphine compounds. The method can obtain the P-N compound under the condition of simple and mild conditions by using two substrates under the condition of an iron catalyst, and the product is obtained with high atom utilization rate and high yield.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention aims to provide a preparation method of a compound containing a P-N bond, which takes a phosphine-containing compound and 3-substituted-1, 4, 2-dioxazole-5-ketone as raw materials to react under the condition of an iron catalyst to generate a compound containing the P-N bond in a formula I, the compound is unstable in column chromatography, a borane complex is added to obtain a compound in a formula II or a compound in a formula III, and the compound in the formula II or the compound in the formula III is stable in air and column chromatography.
The structural formula of the 3-substituted-1, 4, 2-dioxazole-5-ketone is as follows:
wherein R is 1 Selected from alkyl, or alkyl substituted with halogen, alkenyl or hetero atoms, cyclic hydrocarbon or aryl;
the structural formula of the phosphine-containing compound is as follows:
wherein R is 2 、R 3 The same or different, and is independently selected from at least one of alkyl, cyclic hydrocarbon or aryl.
Preferably, the first and second liquid crystal materials are,
the R is 1 Can be selected from any one of the following groups:
the above-mentioned
Any one selected from the following groups:
preferably, the iron catalyst is ferric halide, preferably more than one of ferrous chloride, ferrous chloride tetrahydrate, ferric chloride hexahydrate, ferrous bromide, ferric bromide, ferrous iodide, ferrous fluoride or ferric fluoride; when the anion of the ferric salt is halogen, the reaction is efficient, and other ferric salt reactions can be carried out, such as ferrous sulfate, ferrous acetylacetonate, ferrocene and the like, and corresponding products can also be obtained, but the efficiency is low. This may be the reason for some interaction between the halogen in the iron halide and the secondary phosphine substrate/bisoxazolone.
The solvent used in the reaction is more than one of 1, 2-dichloroethane, dichloromethane, trichloromethane, 1,2, 2-tetrachloroethane, toluene, chlorobenzene, tetrahydrofuran, acetonitrile, diethyl ether or ethyl acetate;
the reaction temperature is room temperature, and the reaction time is 10 minutes to 10 hours.
Preferably, the concentration of the 3-substituted-1, 4, 2-dioxazole-5-ketone is 0.4-4 mol/L; the molar ratio of the phosphine-containing compound to 3-substituted-1, 4, 2-dioxazole-5-one is 1-2: 1; the mol ratio of the iron catalyst to the 3-substituted-1, 4, 2-dioxazole-5-ketone is 0.1-5 percent to 1.
Adding borane complex into the compound of the formula I, and reacting at room temperature for 1-3 hours to obtain a compound of a formula II or a compound of a formula IV correspondingly; the borane complex is one of borane tetrahydrofuran complex and borane dimethyl sulfide complex; the amount is 1-5 equivalents. Preferably, when the compound of the formula II is prepared from the compound of the formula I, the borane complex is prepared in an amount of 1-2 equivalent relative to the 3-substituted-1, 4, 2-dioxazol-5-one; when the compound of formula I is used to prepare the compound of formula IV, the borane complex is used in an amount of 3-5 equivalents relative to the 3-substituted-1, 4, 2-dioxazol-5-one. Equivalents in this context refer to molar ratios.
Another object of the present invention is to provide a compound containing a P-N bond prepared by the process of the first object of the present invention, having the following general structural formula:
A compound of formula I, preferably:
the other purpose of the invention is to provide an amido phosphine or amido phosphine compound containing a P-N bond, which is prepared by the preparation method of the first purpose of the invention and has the following structural general formula:
wherein R is 1 、R 2 、R 3 With 3-substituted-1, 4, 2-dioxazol-5-ones, R in phosphine-containing compounds 1 、R 2 、R 3 The correspondence is the same. At this time.
Preferably, the compound of formula II is:
preferably, the compound of formula iv is:
another object of the present invention is to provide a process for removing R from a P-N compound coordinated with borane which is the object of the present invention 3 P-BH 3 A method for neutralizing borane and a corresponding compound containing P-N.
The reaction steps are as follows: the compound of formula II or IV is added into a reaction flask, dichloromethane or 1, 2-dichloroethane is added under argon, 10 equivalents of triethylamine are added, the reaction is carried out at 55 ℃ for 1 hour, and the solvent is dried by vacuum rotation to obtain the compound of formula I or III without borane (removing borane from phosphorus-containing compounds is a simple and mature method (Synlett,2017,28,221), but a method suitable for the substrate in the present invention is not reported, and the present invention provides an additional feasible method for removing borane).
Preferably, compound P1 gives the decaborane-depleted product P1' in 95% yield under the above conditions.
The compound of formula iii prepared by the above method has the following general structural formula:
Of the compounds of formula iii, preferred are:
another object of the present invention is to provide a compound containing P-N and P ═ N bonds, prepared by the process for the preparation of one of the objects of the present invention, having the following general structural formula:
Wherein R is 1 Preferably any one of the following groups:
compounds of the formula V are particularly preferably:
the fifth object of the present invention is to provide a process for preparing phosphonamides by adding 10 equivalents of 30% H to a compound of formula I 2 O 2 And reacting the aqueous solution for 10 minutes to obtain an oxidized product of the amido phosphine, namely the phosphonamide VI.
Preferably, when R is 2 ＝R 3 Is phenyl, R 1 When being methylThe corresponding phosphonamide product P34 was obtained in 95% yield.
Advantageous effects
The reaction uses simple and easily-obtained iron catalyst, is cheap, environment-friendly and efficient, utilizes simple disubstituted phosphine and 3-substituted-1, 4, 2-dioxazole-5-ketone as reaction substrates, and can obtain various functionalized phosphorus molecules such as amido phosphine I or II, amido phosphine III or IV, phosphonamide VI and imido phosphonamide V by simply changing conditions.
According to the invention, the molar ratio of the phosphine-containing compound to the 3-substituted-1, 4, 2-dioxazole-5-ketone in the reaction raw materials is adjusted, so that the compound containing the P-N bond and the P ═ N bond can be prepared, and the application range of the method is very wide.
The invention can react at room temperature without other reaction conditions such as illumination and the like, and has very mild reaction conditions and very simple and convenient operation.
The invention avoids the use of potentially hazardous azides or toxic phosphine halides and has potential synthetic applications.
The invention adopts disubstituted phosphine to replace trisubstituted phosphine, and the disubstituted phosphine is different from the trisubstituted phosphine in that firstly, the disubstituted phosphine not only has stronger coordination property, but also has stronger P-H reducibility, and the reaction is more difficult to control. Secondly, apparently, the dioxazolone is subjected to insertion reaction with a P-H bond of secondary phosphine to obtain amido phosphine or amino phosphine, but the reaction product still has lone pair electrons and can continuously react with another molecule of dioxazolone to form a diamine product imido phosphonamide, amido phosphine or amino phosphine, and the oxidation can be selectively controlled to be a P ═ O compound, so that abundant P-N compounds can be obtained by controlling the reaction conditions from the secondary phosphine, and the tertiary phosphine can only react with the dioxazolone to obtain a single compound through the lone pair electrons; in terms of reactivity, tertiary phosphines may be converted to P ═ N products by other reactions, such as the classical staudinger reaction, which cannot be applied to secondary phosphine substrates; the reaction product is pentavalent phosphine which reaches a saturated structure and cannot be used as a ligand, while the secondary phosphine product is trivalent phosphine which is a good ligand and has a wider application range.
The molar ratio of the iron catalyst to the 3-substituted-1, 4, 2-dioxazole-5-ketone is 0.1-5%: 1, the addition amount of the iron catalyst is small, and the reaction is efficient; the method adopts secondary phosphine, and has short reaction time and low temperature.
The invention adopts a secondary phosphine substrate, and compounds shown in formula I, formula III and formula V can be used as ligands to coordinate iron catalysts due to the coordination of products, form a competitive relationship with the secondary phosphine substrate, and further reduce the yield of the compounds.
Detailed Description
The invention is further illustrated below with reference to specific examples.
A synthesis method of an amido phosphine compound containing a P-N bond, a compound shown in formula I and a compound shown in formula II has the following reaction general formula:
R 1 is alkyl or aryl, and can be selected from any one of the following groups:
R 2 、R 3 is alkyl or aryl, PR 2 R 3 Can be selected from any one of the following groups:
P1the preparation of (1): ferrous chloride tetrahydrate (0.1 mol%, 2mg) is added into a 100mL reaction flask, 1, 2-dichloroethane (25mL), diphenylphosphine (2 equiv., 21.14mmol, 3.93g), 3-methyl-1, 4, 2-dioxazol-5-one (10.57mmol, 1.067g) are added and reacted at room temperature for 10 hours to obtain a compound P1', the compound is unstable in column chromatography and easy to be oxidized, borane tetrahydrofuran (1.1 equiv) is added and reacted for 30 minutes, a solvent is dried by spinning, and the compound P1 is obtained by column chromatography (95% yield, 2.58 g). The detection data of P1 are as follows: white solid (R) f 0.35, petroleum ether: ethyl acetate ═ 5:1) 1 H NMR(400MHz,CDCl 3 )δ7.84–7.73(m,4H),7.59–7.50(m,2H),7.50–7.40(m,4H),6.43(d,J＝17.4Hz,1H),2.12(s,3H),1.39–0.54(m,3H). 13 C NMR(101MHz,CDCl 3 )δ171.73,171.64,132.95,132.83,132.11,132.08,128.69,128.58,128.21,127.54,24.86,24.83. 31 P NMR(162MHz,CDCl 3 )δ50.39(d,J＝88.4Hz). 11 B NMR(128MHz,CDCl 3 )δ-37.34.HRMS(ESI)m/z Calcd for C 14 H 17 BNNaOP + [M+Na] + :280.1033,found:280.1032.
The presence of P1 is evident from the nuclear magnetic data above, and the presence of P1' is evident to one skilled in the art from the nuclear magnetic data of P1; in addition, the existence of the reaction system P1 ' is verified by other means such as gas chromatography-mass spectrometry (GC-MS), crude nuclear magnetism of the reaction system and the like, because the column chromatography of P1 ' is unstable, the separation process is partially oxidized, and the borane-protected tri-substituted phosphine is mature in the field (Synlett,2017,28,221), so that P1 is prepared by P1 ', and P1 ' is obtained by removing borane from P1 (the nuclear magnetic data verifies, see the preparation of P1 '). Thus, one skilled in the art would be able to determine the presence of P1' by structure with P1, and based on this, one skilled in the art would also be able to reasonably expect that the presence of a compound of formula II would be determined by the structure of formula I, in which case the nuclear magnetic data of formula II would not be provided; the following compounds P2 '-P22' are also not available for the same reason.
Preparation of P2: adding anhydrous ferrous chloride (5 mol%, 1.3mg) into a 100mL reaction flask, adding 1, 2-dichloroethane (0.4mL), diphenylphosphine (2 equiv., 74.4mg), 3- (5-bromopentyl) -1,4, 2-dioxazol-5-one (0.2mmol,47mg), reacting at room temperature for 1 hour to obtain a compound P2', wherein the compound is unstable in column chromatography and easy to oxidize, adding borane dimethylsulfide (1 equiv.), reacting for 40 minutes, spin-drying a solvent, and performing column chromatography to obtain a compound P2 (73% yield, 57.1 mg). P2 is an unknown compound and the assay data is as follows: white solid (R) f 0.52, petroleum ether: ethyl acetate 5:1) 1 H NMR(400MHz,CDCl 3 )δ7.84–7.71(m,4H),7.60–7.50(m,2H),7.50–7.40(m,4H),6.42(d,J＝17.4Hz,1H),3.36(t,J＝6.6Hz,2H),2.36(t,J＝7.4Hz,2H),1.82(p,J＝6.9Hz,2H),1.67–1.53(m,2H),1.47–1.36(m,2H),1.24–0.53(m,3H). 13 C NMR(101MHz,CDCl 3 )δ174.16,174.08,132.94,132.92,132.81,132.13,132.10,128.72,128.61,128.18,127.52,37.32,37.29,33.56,32.37,27.56,24.11. 31 P NMR(162MHz,CDCl 3 )δ50.16(d,J＝60.4Hz). 11 B NMR(128MHz,CDCl 3 )δ-37.27.HRMS(ESI)m/z Calcd for C 18 H 24 BBrNNaOP + [M+Na] + :414.0764,found:414.0766.
Preparation of P3: anhydrous ferrous bromide (5 mol%, 2.2mg) was added to an 8mL reaction flask, methylene chloride (0.5mL), diphenylphosphine (2 eq, 74.4mg), 3- (4-pentynyl) -1,4, 2-dioxazol-5-one (0.2mmol,30.6mg) were added and reacted at room temperature for 30 minutes to give compound P3The compound was unstable to column chromatography and easily oxidized, borane tetrahydrofuran (1 eq) was added, the reaction was carried out for 40 minutes, the solvent was dried by spinning, and column chromatography gave compound P3 (51% yield, 31.5 mg). The detection data of P3 are as follows: white solid (R) f 0.52, petroleum ether: ethyl acetate 5:1) 1 H NMR(400MHz,CDCl 3 )δ7.85–7.69(m,4H),7.59–7.50(m,2H),7.50–7.37(m,4H),6.42(d,J＝17.4Hz,1H),2.50(t,J＝7.3Hz,2H),2.20(td,J＝6.8,2.7Hz,2H),1.97(t,J＝2.6Hz,1H),1.80(p,J＝7.1Hz,2H),1.32–0.47(m,3H). 13 C NMR(101MHz,CDCl 3 )δ173.75,173.67,132.94,132.82,132.13,132.11,128.72,128.60,128.15,127.49,83.02,69.82,35.89,35.86,23.33,17.65. 31 P NMR(162MHz,CDCl 3 )δ50.57(d,J＝82.2Hz). 11 B NMR(128MHz,CDCl 3 )δ-37.19.HRMS(ESI)m/z Calcd for C 18 H 21 BNNaOP + [M+Na] + :332.1346,found:332.1342.
Preparation of P4: anhydrous ferrous iodide (5 mol%, 3.1mg) was added to an 8mL reaction flask, chloroform (0.5mL), diphenylphosphine (2 eq, 74.4mg), 3- (phthalimide) -1,4, 2-dioxazol-5-one (0.2mmol,54.8mg) were added, and the reaction was carried out at room temperature for 1 hour to obtain compound P4', which was unstable in column chromatography and easily oxidized, borane tetrahydrofuran (1 eq) was added, the reaction was carried out for 20 minutes, the solvent was spin-dried, and the compound P4 (95% yield, 79.8mg) was obtained by column chromatography. The detection data of P4 are as follows: white solid (R) f 0.24, petroleum ether: ethyl acetate 5:1) 1 H NMR(400MHz,CDCl 3 )δ7.79(dd,J＝5.4,3.1Hz,2H),7.77–7.66(m,4H),7.60–7.45(m,3H),7.45–7.36(m,2H),7.36–7.28(m,1H),7.14(td,J＝7.8,2.8Hz,2H),6.56(d,J＝17.3Hz,1H),4.84–4.69(m,1H),3.30(dd,J＝15.3,9.6Hz,1H),2.85(dd,J＝15.3,6.1Hz,1H),1.42(d,J＝6.9Hz,3H),1.22–0.40(m,3H). 13 C NMR(101MHz,CDCl 3 )δ171.55,171.47,168.18,134.12,134.09,132.98,132.86,132.61,132.49,132.06,132.03,131.85,131.80,131.77,128.62,128.51,128.39,128.28,128.05,127.98,127.39,127.32,123.45,44.00,41.27,41.24,18.95. 31 P NMR(162MHz,CDCl 3 )δ50.98(d,J＝50.3Hz). 11 B NMR(128MHz,CDCl 3 )δ-37.32.HRMS(ESI)m/z Calcd for C 24 H 24 BN 2 NaO 3 P + [M+Na] + :453.1510,found:453.1509.
Preparation of P5: ferric chloride hexahydrate (5 mol%, 2.7mg) is added into an 8mL reaction flask, 1, 2-dichloroethane (0.5mL), diphenylphosphine (2 equiv., 74.4mg), 3- (styryl) -1,4, 2-dioxazol-5-one (0.2mmol,37.8mg) are added, and the reaction is carried out at room temperature for 20 minutes to obtain a compound P5', wherein the compound is unstable in column chromatography and easy to oxidize, borane tetrahydrofuran (1 equiv) is added, the reaction is carried out for 15 minutes, a solvent is dried by spinning, and the compound P5 (65% yield, 44.9mg) is obtained by column chromatography. The detection data of P5 are as follows: white solid (R) f 0.59, petroleum ether: ethyl acetate 5:1) 1 H NMR(400MHz,CDCl 3 )δ7.84(dd,J＝12.2,7.5Hz,4H),7.63(d,J＝15.6Hz,1H),7.58–7.52(m,2H),7.51–7.43(m,6H),7.42–7.33(m,3H),6.64–6.47(m,2H),1.56–0.53(m,3H). 13 C NMR(101MHz,CDCl 3 )δ166.55,145.14,134.00,133.07,132.95,132.17,132.14,130.84,129.14,128.76,128.65,128.38,128.24,127.57,119.26,119.21. 31 P NMR(162MHz,CDCl 3 )δ51.04(d,J＝69.4Hz). 11 B NMR(128MHz,CDCl 3 )δ-37.09.HRMS(ESI)m/z Calcd for C 21 H 21 BNNaOP + [M+Na] + :368.1346,found:368.1342.
Preparation of P6: iron fluoride (5 mol%, 1.1mg) was added to an 8mL reaction flask, and 1, 2-dichloroethane (0.5mL), diphenylphosphine (2 eq, 74.4mg), 3- (cyclopentylmethyl) -1,4, 2-dioxazol-5-one (0.2mmol,33.8mg) were added at room temperatureAfter 30 minutes of reaction, compound P6' is obtained, which is unstable in column chromatography and easily oxidized, borane tetrahydrofuran (1 equivalent) is added for 1 hour of reaction, the solvent is dried by spinning, and the compound P6 is obtained by column chromatography (71% yield, 46.2 mg). P6 is an unknown compound and the assay data is as follows: white solid (R) f 0.66, petroleum ether: ethyl acetate 5:1) 1 H NMR(400MHz,CDCl 3 )δ7.78(dd,J＝12.2,7.6Hz,4H),7.56–7.49(m,2H),7.49–7.37(m,4H),6.37(d,J＝17.7Hz,1H),2.33(d,J＝7.4Hz,2H),2.25–2.10(m,1H),1.84–1.71(m,2H),1.67–1.45(m,4H),1.18–1.05(m,2H),1.04–0.33(m,3H). 13 C NMR(101MHz,CDCl 3 )δ174.21,174.12,132.97,132.85,132.03,132.01,128.65,128.54,128.40,127.74,43.97,43.95,36.88,32.50,25.06. 31 P NMR(162MHz,CDCl 3 )δ50.10(d,J＝83.7Hz). 11 B NMR(128MHz,CDCl 3 )δ-37.16.HRMS(ESI)m/z Calcd for C 19 H 25 BNNaOP + [M+Na] + :348.1659,found:348.1658.
Preparation of P7: ferrous chloride tetrahydrate (5 mol%, 2.0mg) is added into an 8mL reaction flask, 1, 2-dichloroethane (0.5mL), diphenylphosphine (2 equiv., 74.4mg), 3- (cyclohexyl) -1,4, 2-dioxazol-5-one (0.2mmol,33.8mg) are added, and the reaction is carried out for 1 hour at room temperature, so as to obtain a compound P7', the compound is unstable in column chromatography and easy to oxidize, borane tetrahydrofuran (1 equiv) is added, the reaction is carried out for 30 minutes, a solvent is dried in a spinning mode, and the compound P7 (68% yield, 44.2mg) is obtained through column chromatography. P7 is an unknown compound and the assay data is as follows: white solid (R) f 0.72, petroleum ether: ethyl acetate 5:1) 1 H NMR(400MHz,CDCl 3 )δ7.76(dd,J＝12.2,7.7Hz,4H),7.52(t,J＝7.4Hz,2H),7.48–7.39(m,,4H),6.29(d,J＝17.7Hz,1H),2.25(t,J＝11.5Hz,1H),1.93–1.82(m,2H),1.82–1.71(m,2H),1.70–1.62(m,1H),1.45–1.19(m,5H),0.86(m,3H). 13 C NMR(101MHz,CDCl 3 )δ177.30,132.89,132.77,131.99,131.97,128.66,128.55,128.38,127.71,46.21,46.18,29.39,25.61,25.54,25.47. 31 P NMR(162MHz,CDCl 3 )δ49.70(d,J＝82.5Hz). 11 B NMR(128MHz,CDCl 3 )δ-37.13.HRMS(ESI)m/z Calcd for C 19 H 25 BNNaOP + [M+Na] + :348.1659,found:348.1655.
Preparation of P8: anhydrous ferric bromide (5 mol%, 3mg) was added to an 8mL reaction flask, acetonitrile (0.5mL), diphenylphosphine (2 eq, 74.4mg), 3- (4-iodophenyl) -1,4, 2-dioxazol-5-one (0.2mmol,57.8mg) were added, and the reaction was carried out at room temperature for 1 hour to give compound P8', which was unstable in column chromatography and easily oxidized, borane tetrahydrofuran (1 eq) was added, and the reaction was carried out for 40 minutes, followed by spin-drying of the solvent and column chromatography to give compound P8 (85% yield, 75.7 mg). P8 is an unknown compound and the assay data is as follows: white solid (R) f 0.72, petroleum ether: ethyl acetate ═ 5:1) 1 H NMR(400MHz,CDCl 3 )δ7.91–7.76(m,6H),7.59–7.51(m,4H),7.51–7.42(m,4H),6.88(d,J＝16.7Hz,1H),1.53–0.59(m,3H). 13 C NMR(101MHz,CDCl 3 )δ167.17,167.09,138.31,133.10,132.97,132.31,132.29,132.10,129.24,128.82,128.70,127.83,127.17,100.78. 31 P NMR(162MHz,CDCl 3 )δ52.62(d,J＝77.2Hz). 11 B NMR(128MHz,CDCl 3 )δ-37.17.HRMS(ESI)m/z Calcd for C 19 H 18 BINNaOP + [M+Na] + :468.0156,found:468.0156.
Preparation of P9: ferrous chloride tetrahydrate (5 mol%, 2.0mg) is added into an 8mL reaction flask, toluene (0.5mL), bis- (3, 5-dimethylphenyl) phosphine (2 equiv., 96.8mg), 3-methyl-1, 4, 2-dioxazol-5-one (0.2mmol,20.2mg) are added, and the reaction is carried out at room temperature for 0.5 hour to obtain a compound P9', wherein the compound has unstable column chromatography and is easy to be oxidized, borane tetrahydrofuran (1 equiv) is added, and the reaction is carried out for 20 minutesThe solvent was dried by evaporation and column chromatography gave compound P9 (80% yield, 50 mg). P9 is an unknown compound and the assay data is as follows: white solid (R) f 0.4, petroleum ether: ethyl acetate 5:1) 1 H NMR(400MHz,CDCl 3 )δ7.45–7.36(m,4H),7.18(s,2H),6.43(d,J＝16.3Hz,1H),2.36(s,12H),2.15(d,J＝1.1Hz,3H),1.24–0.55(m,3H). 13 C NMR(101MHz,CDCl 3 )δ171.61,138.33,138.21,133.96,133.93,133.39,130.36,130.24,128.46,128.34,128.02,127.37,24.92,24.89,21.48,21.41. 31 P NMR(162MHz,CDCl 3 )δ50.25. 11 B NMR(128MHz,CDCl 3 )δ-36.80.HRMS(ESI)m/z Calcd for C 18 H 25 BNNaOP + [M+Na] + :336.1659,found:336.1655.
Preparation of P10: ferrous fluoride (5 mol%, 0.9mg) is added into an 8mL reaction flask, 1, 2-dichloroethane (0.5mL), isopropylphenylphosphine (2 equivalents, 60.8mg), 3-methyl-1, 4, 2-dioxazol-5-one (0.2mmol,20.2mg) are added, and the reaction is carried out for 1 hour at room temperature, thus obtaining a compound P10', which has unstable column chromatography and is easy to be oxidized, borane tetrahydrofuran (1 equivalent) is added, the reaction is carried out for 10 minutes, a solvent is dried by spinning, and the column chromatography is carried out, thus obtaining a compound P10 (82% yield, 44.1 mg). P10 is an unknown compound and the assay data is as follows: white solid (R) f 0.48, petroleum ether: ethyl acetate 5: 1). 1 H NMR(400MHz,CDCl 3 )δ8.11–7.98(m,2H),7.58–7.49(m,1H),7.45(t,J＝7.6Hz,2H),6.15(d,J＝15.3Hz,1H),3.62–3.32(m,1H),2.07(s,3H),1.35–1.19(m,3H),1.06–0.92(m,3H),0.95–0.17(m,3H). 13 C NMR(101MHz,CDCl 3 )δ172.67,133.27,133.16,132.39,132.37,128.64,128.54,128.28,127.70,24.83,24.79,22.04,21.62,16.11,15.98,15.90. 31 P NMR(162MHz,CDCl 3 )δ62.92(d,J＝87.8Hz). 11 B NMR(128MHz,CDCl 3 )δ-42.80.HRMS(ESI)m/z Calcd for C 14 H 29 BNNaOP + [M+Na] + :292.1972,found:292.1971.
Preparation of P11: anhydrous iron fluoride (5 mol%, 1.1mg) was added to an 8mL reaction flask, tetrachloroethane (0.5mL), dicyclohexylphosphine (2 eq, 79.2mg), 3-methyl-1, 4, 2-dioxazol-5-one (0.2mmol,20.2mg) were added, and the reaction was carried out at room temperature for 1 hour to obtain compound P11', which was unstable in column chromatography and easily oxidized, borane tetrahydrofuran (1 eq) was added, the reaction was carried out for 30 minutes, the solvent was spin-dried, and the compound P11 (66% yield, 29.4mg) was obtained by column chromatography. P11 is an unknown compound and the assay data is as follows: white solid (R) f 0.52, petroleum ether: ethyl acetate 5: 1). 1 H NMR(400MHz,CDCl 3 )δ5.73(d,J＝13.7Hz,1H),2.54–2.38(m,2H),2.11(s,3H),1.91–1.76(m,6H),1.76–1.65(m,4H),1.57–1.44(m,2H),1.42–1.18(m,8H),0.78–0.01(m,3H). 13 C NMR(101MHz,CDCl 3 )δ172.87,172.78,32.94,32.59,26.95,26.92,26.65,26.59,26.54,26.51,26.48,26.44,25.89,25.88,24.66,24.63. 31 P NMR(162MHz,CDCl 3 )δ70.85(d,J＝88.3Hz). 11 B NMR(128MHz,CDCl 3 )δ-42.98.HRMS(ESI)m/z Calcd for C 11 H 19 BNNaOP + [M+Na] + :246.1190,found:246.1187.
Preparation of P12: adding anhydrous ferrous bromide (5 mol%, 2.2mg) into an 8mL reaction flask, adding 1, 2-dichloroethane (1mL), di-tert-butylphosphine (2 equivalents, 58.4mg), 3-methyl-1, 4, 2-dioxazol-5-one (0.2mmol,20.2mg), reacting at room temperature for 1 hour to obtain a compound P12', wherein the compound is unstable in column chromatography and easy to oxidize, adding borane tetrahydrofuran (1 equivalent), reacting for 1 hour, spin-drying a solvent, and performing column chromatography to obtain a compound P12 (51% yield, 22.1 mg). P12 is an unknown compound and the assay data is as follows: white solid (R) f 0.6, petroleum ether: ethyl acetate 5: 1). 1 H NMR(400MHz,CDCl 3 )δ5.77(d,J＝10.8Hz,1H),2.14(s,3H),1.38(d,J＝14.5Hz,18H),0.94–0.07(m,3H). 13 C NMR(101MHz,CDCl 3 )δ172.67,35.85,35.59,28.09,28.06,24.97,24.94. 31 P NMR(162MHz,CDCl 3 )δ89.20(d,J＝105.3Hz). 11 B NMR(128MHz,CDCl 3 )δ-39.33.HRMS(ESI)m/z Calcd for C 10 H 25 BNNaOP + [M+Na] + :240.1659,found:240.1658.
A method for synthesizing compounds of formula I and formula IV containing P-N bonds has the following reaction general formula:
wherein R is 1 Is alkyl or aryl, and can be selected from any one of the following groups:
R 2 、R 3 is alkyl or aryl, PR 2 R 3 Can be selected from any one of the following groups:
preparation of P13: anhydrous ferrous chloride (5 mol%, 2.6mg) was added to an 8mL reaction flask, 1, 2-dichloroethane (1mL), diphenylphosphine (2 eq, 128.8mg), 3-methyl-1, 4, 2-dioxazol-5-one (0.4mmol,40.4mg) were added and reacted at room temperature for 1 hour to give compound P1', borane tetrahydrofuran (3 eq) was added and reacted for 3 hours, the solvent was spin-dried and column chromatography was performed to give compound P13 (81% yield, 78.7 mg). P13 is an unknown compound and the assay data is as follows: white solid (R) f ＝0.48,Petroleum ether: ethyl acetate 20: 1). 1 H NMR(400MHz,CDCl 3 )δ7.71–7.59(m,4H),7.53–7.38(m,6H),2.93(q,J＝6.8Hz,2H),2.16–2.00(m,1H),1.15–1.45(m,1H),1.10(t,J＝7.1Hz,3H),1.41–0.46(m,2H). 13 C NMR(101MHz,CDCl 3 )δ132.06,131.95,131.30,131.27,128.69,128.59,37.92,37.88,17.64,17.58. 31 P NMR(162MHz,CDCl 3 )δ56.96–52.72(m). 11 B NMR(128MHz,CDCl 3 )δ-37.92.HRMS(ESI)m/z Calcd for C 14 H 19 BNNaP + [M+Na] + :266.1240,found:266.1237.
The standard conditions described above are those described in the text of the preparation of p13 above.
Preparation of P14: anhydrous ferrous chloride (5 mol%, 1.3mg) was added to an 8mL reaction flask, 1, 2-dichloroethane (0.5mL), diphenylphosphine (2 eq, 74.4mg), 3- (5-bromopentyl) -1,4, 2-dioxazol-5-one (0.2mmol,47mg) were added and reacted at room temperature for 1 hour to give compound P2', borane tetrahydrofuran (5 eq) was added and reacted for 3 hours, solvent was spin dried and column chromatography was performed to give compound P14 (60% yield, 45.2 mg). P14 is an unknown compound and the assay data is as follows: white solid (R) f 0.45, petroleum ether: ethyl acetate 20: 1). 1 H NMR(400MHz,CDCl 3 )δ7.70–7.59(m,4H),7.54–7.40(m,6H),3.35(t,J＝6.8Hz,2H),2.90(p,J＝7.1Hz,2H),2.11(q,J＝7.1Hz,1H),1.86–1.72(m,2H),1.51–1.40(m,2H),1.40–1.31(m,2H),1.31–1.23(m,2H),1.17–0.43(m,3H). 13 C NMR(101MHz,CDCl 3 )δ132.06,132.02,131.95,131.40,131.36,131.34,128.72,128.62,42.89,42.86,33.88,32.63,31.94,31.88,27.80,25.83. 31 P NMR(162MHz,CDCl 3 )δ55.30(d,J＝94.0Hz). 11 B NMR(128MHz,CDCl 3 )δ-38.02.HRMS(ESI)m/z Calcd for C 18 H 26 BBrNNaP + [M+Na] + :400.0972,found:400.0970.
Preparation of P15: anhydrous ferrous iodide (5 mol%, 3.1mg) was added to an 8mL reaction flask, chloroform (0.5mL), diphenylphosphine (2 eq, 74.4mg)3- (2-phthalimidopropyl) -1,4, 2-dioxazol-5-one (0.2mmol,54.8mg) was added, and the reaction was carried out at room temperature for 1 hour to obtain compound P4', borane tetrahydrofuran (3 eq) was added, the reaction was carried out for 3 hours, the solvent was spin-dried, and column chromatography was carried out to obtain compound P15 (60% yield, 50 mg). P15 is an unknown compound and the assay data is as follows: white solid (R) f 0.14, petroleum ether: ethyl acetate 20: 1). 1 H NMR(400MHz,CDCl 3 )δ7.84–7.77(m,2H),7.75–7.68(m,2H),7.68–7.55(m,4H),7.51–7.34(m,6H),4.49–4.31(m,1H),3.10–2.76(m,2H),2.53–2.38(m,1H),2.24–2.10(m,1H),1.89–1.74(m,1H),1.41(d,J＝7.0Hz,3H),1.17–0.46(m,3H). 13 C NMR(101MHz,CDCl 3 )δ168.68,134.14,131.93,131.92,131.83,131.81,131.37,131.34,131.31,128.77,128.73,128.67,128.63,123.32,44.60,40.09,35.97,35.92,18.71. 31 P NMR(162MHz,CDCl 3 )δ56.15(d,J＝93.6Hz). 11 B NMR(128MHz,CDCl 3 )δ-38.77.HRMS(ESI)m/z Calcd for C 24 H 26 BN 2 NaO 2 P + [M+Na] + :439.1717,found:439.1719.
Preparation of P16: adding anhydrous ferrous fluoride (5 mol%, 0.9mg) into an 8mL reaction bottle, adding 1, 2-dichloroethane (0.5mL), diphenylphosphine (2 equiv., 74.4mg), 3- (cyclopentylmethyl) -1,4, 2-dioxazol-5-one (0.2mmol,33.8mg), reacting at room temperature for 1 hour to obtain a compound P6', adding borane tetrahydrofuran (5 equiv.), reacting for 3 hours, spin-drying a solvent, and performing column chromatography to obtain a compound P6Substance P16 (70% yield, 43.5 mg). P16 is an unknown compound and the assay data is as follows: white solid (R) f 0.59, petroleum ether: ethyl acetate 20: 1). 1 H NMR(400MHz,CDCl 3 )δ7.72–7.60(m,4H),7.54–7.39(m,6H),2.89(p,J＝6.9Hz,2H),2.09(s,1H),1.81–1.61(m,3H),1.58–1.51(m,2H),1.50–1.41(m,2H),4H),1.04–0.93(m,2H),0.92–0.51(m,3H). 13 C NMR(101MHz,CDCl 3 )δ132.20,132.12,132.02,131.57,131.29,131.27,128.70,128.60,42.48,42.44,38.67,38.62,37.46,32.66,25.14. 31 P NMR(162MHz,CDCl 3 )δ55.25(d,J＝95.0Hz). 11 B NMR(128MHz,CDCl 3 )δ-38.05.HRMS(ESI)m/z Calcd for C 19 H 27 BNNaP + [M+Na] + :334.1866,found:334.1862.
Preparation of P17: ferrous chloride tetrahydrate (5 mol%, 2.0mg) is added into an 8mL reaction flask, 1, 2-dichloroethane (0.5mL), diphenylphosphine (2 equiv., 74.4mg), 3- (cyclohexyl) -1,4, 2-dioxazol-5-one (0.2mmol,33.8mg) are added and reacted at room temperature for 1 hour to obtain a compound P7', borane tetrahydrofuran (5 equiv.) is added and reacted for 3 hours, a solvent is dried by spinning, and column chromatography is carried out to obtain a compound P17 (55% yield, 34.2 mg). P17 is an unknown compound and the assay data is as follows: white solid (R) f 0.62, petroleum ether: ethyl acetate 20: 1). 1 H NMR(400MHz,CDCl 3 )δ7.72–7.58(m,4H),7.54–7.39(m,6H),2.71(t,J＝6.7Hz,2H),2.13(s,1H),1.75–1.58(m,4H),1.35–1.26(m,1H),1.24–1.04(m,4H),0.89–0.75(m,2H). 13 C NMR(101MHz,CDCl 3 )δ132.18,132.11,132.07,131.48,131.32,131.29,128.70,128.60,49.41,49.37,39.81,39.75,30.82,26.54,25.95. 31 P NMR(162MHz,CDCl 3 )δ55.27(d,J＝100.8Hz). 11 B NMR(128MHz,CDCl 3 )δ-38.13.HRMS(ESI)m/z Calcd for C 19 H 27 BNNaP + [M+Na] + :334.1866,found:334.1862.
Preparation of P18: anhydrous ferrous bromide (5 mol%, 2.2mg) was added to an 8mL reaction flask, acetonitrile (0.5mL), diphenylphosphine (2 eq, 74.4mg), 3- (4-iodophenyl) -1,4, 2-dioxazol-5-one (0.2mmol,57.8mg) were added, and the reaction was carried out at room temperature for 1 hour to give compound P8', borane tetrahydrofuran (5 eq) was added, and the reaction was carried out for 3 hours, followed by spin-drying of the solvent and column chromatography to give compound P18 (66% yield, 56.9 mg). P18 is an unknown compound and the assay data is as follows: white solid (R) f 0.45, petroleum ether: ethyl acetate 20: 1). 1 H NMR(400MHz,CDCl 3 )δ7.72–7.62(m,4H),7.62–7.55(m,2H),7.54–7.47(m,2H),7.47–7.39(m,4H),7.03–6.89(m,2H),4.05(t,J＝7.1Hz,2H),2.44(q,J＝6.7Hz,1H),1.46–0.52(m,3H). 13 C NMR(101MHz,CDCl 3 )δ139.38,137.72,132.03,131.92,131.75,131.58,131.55,131.13,128.86,92.92,46.50,46.48. 31 P NMR(162MHz,CDCl 3 )δ57.17(d,J＝91.1Hz). 11 B NMR(128MHz,CDCl 3 )δ-38.24.HRMS(ESI)m/z Calcd for C 19 H 20 BINNaP + [M+Na] + :454.0363,found:454.0360.
Preparation of P19: ferrous chloride tetrahydrate (5 mol%, 2.0mg) is added into an 8mL reaction flask, toluene (0.5mL), bis- (3, 5-dimethylphenyl) phosphine (2 equiv., 96.8mg), 3-methyl-1, 4, 2-dioxazol-5-one (0.2mmol,20.2mg) are added and reacted for 1 hour at room temperature to obtain a compound P9', borane tetrahydrofuran (5 equiv.) is added and reacted for 3 hours, a solvent is dried in a rotary manner, and column chromatography is carried out to obtain a compound P19 (66% yield, 39.5 mg). P19 is an unknown compound and the assay data is as follows: white solid (R) f 0.66, petroleum ether: ethyl acetate 20: 1). 1 H NMR(400MHz,CDCl 3 )δ7.25(d,J＝11.2,4H),7.11(s,2H),2.93(p,J＝7.1Hz,2H),2.33(s,12H),1.97(s,1H),1.11(t,J＝7.1Hz,3H),1.30–0.39(m,3H). 13 C NMR(101MHz,CDCl 3 )δ138.26,138.16,133.04,133.01,131.92,131.30,129.55,37.88,37.85,21.48,17.69,17.63. 31 P NMR(162MHz,CDCl 3 )δ54.51(d,J＝101.6Hz). 11 B NMR(128MHz,CDCl 3 )δ-37.88.HRMS(ESI)m/z Calcd for C 18 H 27 BNNaP + [M+Na] + :322.1866,found:322.1864.
Preparation of P20: anhydrous ferrous fluoride (5 mol%, 0.9mg) was added to an 8mL reaction flask, 1, 2-dichloroethane (0.5mL), isopropylphenylphosphine (2 eq, 60.8mg), 3-methyl-1, 4, 2-dioxazol-5-one (0.2mmol,20.2mg) were added and reacted at room temperature for 1 hour to give compound P10', borane tetrahydrofuran (5 eq) was added and reacted for 3 hours, solvent was spin-dried, and column chromatography was performed to give compound P20 (72% yield, 36.7 mg). P20 is an unknown compound and the assay data is as follows: white solid (R) f 0.58, petroleum ether: ethyl acetate 20: 1). 1 H NMR(400MHz,CDCl 3 )δ7.76–7.63(m,2H),7.56–7.34(m,3H),3.05–2.83(m,2H),2.37–2.19(m,1H),1.74(s,1H),1.23–0.98(m,9H),0.91–0.22(m,3H). 13 C NMR(101MHz,CDCl 3 )δ132.11,131.59,131.25,131.16,131.05,131.02,128.66,128.56,37.44,25.82,25.38,17.99,17.93,16.32,16.28,16.16. 31 P NMR(162MHz,CDCl 3 )δ63.94(dd,J＝140.7,63.7Hz). 11 B NMR(128MHz,CDCl 3 )δ-41.77.HRMS(ESI)m/z Calcd for C 14 H 31 BNNaP + [M+Na] + :278.2179,found:278.2179.
Preparation of P21: ferrous chloride tetrahydrate (5 mol%, 2.0mg) was charged into an 8mL reaction flask, 1, 2-dichloroethane (0.5mL), dicyclohexylphosphine (2 eq, 79.2mg), 3-methyl-1, 4, 2-dioxazol-5-one (0.2mmol,20.2mg) were added, and the mixture was reacted at room temperature for 1 hour to obtain Compound P11'Borane tetrahydrofuran (5 eq) was added and the reaction was run for 1 hour, solvent dried and column chromatographed to give compound P21 (54% yield, 22.7 mg). P21 is an unknown compound and the assay data is as follows: white solid (R) f 0.85, petroleum ether: ethyl acetate 20: 1). 1 H NMR(400MHz,CDCl 3 )δ2.95(p,J＝7.1Hz,2H),1.91–1.61(m,12H),1.47–1.13(m,11H),1.09(t,J＝7.1Hz,3H),0.81–0.01(m,3H). 13 C NMR(101MHz,CDCl 3 )δ38.18,34.14,33.76,26.99,26.89,26.77,26.48,26.25,25.93,25.90,18.46. 31 P NMR(162MHz,CDCl 3 )δ67.92(dd,J＝146.1,57.0Hz). 11 B NMR(128MHz,CDCl 3 )δ-43.23.HRMS(ESI)m/z Calcd for C 11 H 22 BNP + [M+H] + :210.1577,found:210.1576.
Preparation of P22: anhydrous ferrous bromide (5 mol%, 2.2mg) was added to an 8mL reaction flask, 1, 2-dichloroethane (0.5mL), di-tert-butylphosphine (0.2mmol,58.4mg), 3-methyl-1, 4, 2-dioxazol-5-one (0.5mmol,50.5mg) were added and reacted at room temperature for 1 hour to give compound P12', borane tetrahydrofuran (5 eq) was added and reacted for 1 hour, the solvent was spin-dried, and column chromatography was performed to give compound P22 (45% yield, 18.3 mg). P22 is an unknown compound and the assay data is as follows: white solid (R) f 0.65, petroleum ether: ethyl acetate 20: 1). 1 H NMR(400MHz,CDCl 3 )δ3.11(p,J＝7.0Hz,2H),1.34(s,1H),1.23(d,J＝12.9Hz,18H),1.16–1.09(m,3H),0.89–0.02(m,3H). 13 C NMR(101MHz,CDCl 3 )δ39.51,35.14,34.82,27.31,27.29,18.67,18.62. 31 P NMR(162MHz,CDCl 3 )δ82.91(dd,J＝141.8,68.0Hz). 11 B NMR(128MHz,CDCl 3 )δ-43.31(qd,J＝95.3,71.8Hz).HRMS(ESI)m/z Calcd for C 10 H 27 BNNaP + [M+Na] + :226.1866,found:226.1866.
The products P13-P22 of the invention can also be prepared by the same procedure as described above, except that the borane compound is added in two portionsAdding, for example, a borane in an amount of 1 to 2 to the intermediate of the compound of the formula I to obtain a compound of the formula II, and further adding a borane in an amount of 1 to 4 equivalents to the intermediate of the compound of the formula II to obtain a compound of the formula IV; by de-R as described below 3 P-BH 3 The compound of formula IV can be obtained by a borane neutralization method. Therefore, the compound of formula III can be prepared from the compounds of formula I, formula II and formula IV of the invention.
Remove R 3 P-BH 3 A process for neutralizing borane, having the formula:
the reaction steps are as follows: the compound of formula II or IV is added into a reaction flask, dichloromethane or 1, 2-dichloroethane is added under argon, 10 equivalents of triethylamine are added, the reaction is carried out at 55 ℃ for 1 hour, and the solvent is dried by vacuum rotation to obtain the compound of formula I or II without borane (removing borane from phosphorus-containing compounds is a simple and mature method (Synlett,2017,28,221), but a method suitable for the substrate in the present invention is not reported, and the present invention provides an additional feasible method for removing borane).
The compound of formula iii prepared by the above method has the following general structural formula:
Of the compounds of formula iii, preferred are:
the unstable cause type column chromatography separation process of the formula I or the formula III is easy to oxidize, and the air oxidation is relatively slow; the method for removing the borane does not need purification, the reaction system can be dried by spinning, and a small amount of Et is generated 3 N-BH 3 The residue, which is not harmful, can also be removed by recrystallization, so that this process gives pure compounds of the formula I or III.
Preferably, compound P1 gives the decaborane-depleted product P1' in 95% yield under the above conditions.
Preferably, when R is 2 ＝R 3 Is phenyl, R 1 (methyl), the corresponding borane-removed amidophosphine compound P1' (R removal as described above) was obtained in 95% yield 3 P-BH 3 The borane removal method belongs to the methods commonly used in the field, and a person skilled in the art can foresee that the compound in the formula II can effectively remove the borane to obtain the compound in the formula I; it is also envisioned by those skilled in the art that the compounds of formula iv can be effectively borane-free to give compounds of formula iii).
Preparation of P1' (borane removal): in a glove box, compound P1(0.2mmol, 51.4mg) was charged into an 8mL reaction flask, 1, 2-dichloroethane (0.5mL) and triethylamine (10 eq, 202mg) were added in that order, the reaction was heated to 55 degrees celsius, reacted for 1 hour, and the solvent was dried by spinning to give compound P1' (95% yield, 46.2 mg). And a small amount of residual triethylamine can be removed by recrystallization. The P1' monitoring data are as follows. White solid (R) f 0.2, petroleum ether: ethyl acetate 5: 1). 1 H NMR(400MHz,CDCl 3 )δ7.50–7.30(m,10H),6.00(brs,1H),2.31and 2.13(2×s,3H). 13 C NMR(101MHz,CDCl 3 )δ175.74,175.51,173.51,173.39,138.25,131.83,131.62,131.38,131.17,129.96,129.72,128.93,128.83,128.76,24.70,21.75,21.60. 31 P NMR(162MHz,CDCl 3 )δ30.87,22.43.
An imido phosphonamide compound V containing P-N and P ═ N bonds and a synthesis method thereof have the following reaction general formula:
at the moment, the molar ratio of the phosphine-containing compound to the 3-substituted-1, 4, 2-dioxazole-5-one in the reaction raw materials is 1: 2.5.
the compound of the formula V can be used as an N-N bidentate ligand to form a four-membered ring complex with metal, and can be potentially applied to transfer hydrogenation (Dalton Trans.2020,49,1473.) or coupling reaction (Russ. chem.Bull.,2014,63,2305)
The following is the preparation procedure for each specific example:
preparation of P23: in a glovebox, anhydrous ferrous bromide (0.5 mol%, 6.0mg) was added to a 100mL reaction flask, at which time the iron catalyst was based on the phosphine-containing compound; 1, 2-dichloroethane (15mL), 3-methyl-1, 4, 2-dioxazol-5-one (15mmol,1.5g,2.5 equiv.), diphenylphosphine (6mmol, 1.12g) were sequentially added to react at room temperature for 3 hours, and the solvent was dried by spinning, and column chromatography gave compound P23 (94% yield, 1.7 g). P23 is an unknown compound and the assay data is as follows: white solid (R) f 0.18,100% ethyl acetate). 1 H NMR(400MHz,CDCl 3 )δ9.84(brs,1H),7.90–7.81(m,4H),7.62–7.54(m,2H),7.52–7.42(m,4H),2.14(d,J＝2.2Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ178.12,178.04,132.94,132.91,132.52,132.40,128.58,128.58,128.44,127.59,126.35,26.53,26.40. 31 P NMR(162MHz,CDCl 3 )δ23.03.HRMS(ESI)m/z Calcd for C 16 H 18 N 2 O 2 P + [M+H] + :301.1100,found:301.1099.
Preparation of P24: in a glove box, anhydrous ferrous iodide (5 mol%, 2.2mg) was added to an 8mL reaction flask, and diethyl ether (0.5mL), 3- (5-bromopentyl) -1,4, 2-dioxazol-5-one (0.5mmol, 2.5 equiv, 117.5mg), diphenylphosphine (0.2mmol, 37.2mg) were sequentially added, reacted at room temperature for 1 hour, the solvent was spin-dried, and column chromatography was performed to obtain compound P24 (74% yield, 84.2 mg). P24 is an unknown compound and the assay data is as follows: white solid (R) f 0.18, petroleum ether: ethyl acetate 2: 1). 1 H NMR(400MHz,CDCl 3 )δ9.98(brs,1H),7.91–7.79(m,4H),7.63–7.54(m,2H),7.53–7.44(m,7.91–7.79(m,4H),3.36(t,J＝6.8Hz,4H),2.41(t,J＝7.4Hz,4H),1.84(p,J＝7.0Hz,4H),1.66(p,J＝7.5Hz,4H),1.50–1.36(m,4H). 13 C NMR(101MHz,CDCl 3 )δ180.42,132.98,132.95,132.43,132.32,128.60,128.46,127.68,126.44,39.10,38.97,33.65,32.42,27.66,24.67. 31 P NMR(162MHz,CDCl 3 )δ23.58.HRMS(ESI)m/z Calcd for C 24 H 32 Br 2 N 2 O 2 P + [M+H] + :569.0563,found:569.0561.
Preparation of P25: in a glove box, anhydrous ferrous chloride (5 mol%, 1.6mg) was added to an 8mL reaction flask, tetrahydrofuran (0.5mL), 3- (4-pentynyl) -1,4, 2-dioxazol-5-one (0.5mmol, 2.5 equiv., 76.5mg), diphenylphosphine (0.2mmol, 37.2mg) were sequentially added, and the reaction was carried out at room temperature for 1 hour, followed by spin-drying the solvent and column chromatography to obtain compound P25 (41% yield, 33.2 mg). P25 is an unknown compound and the assay data is as follows: white solid (R) f 0.45,100% ethyl acetate). 1 H NMR(400MHz,CDCl 3 )δ7.89–7.79(m,4H),7.59(td,J＝7.3,1.6Hz,2H),7.52–7.44(m,4H),2.53(t,J＝7.4Hz,4H),2.21(td,J＝7.0,2.7Hz,4H),1.94(t,J＝2.6Hz,2H),1.84(p,J＝7.2Hz,4H). 13 C NMR(101MHz,CDCl 3 )δ179.93,133.16,133.13,132.60,132.49,131.92,131.80,128.77,128.63,127.80,126.55,83.74,69.13,38.07,37.94,24.30,17.98. 31 P NMR(162MHz,CDCl 3 )δ23.51.HRMS(ESI)m/z Calcd for C 24 H 26 N 2 O 2 P + [M+H] + :405.1726,found:405.1723.
Preparation of P26: in a glove box, ferrous chloride tetrahydrate (5 mol%, 2.0mg) was charged into an 8mL reaction flask, followed by the addition of toluene (0.5mL), 3- (cyclopentylmethyl) -1,4, 2-dioxazol-5-one (0.5mmol, 2.5 equiv, 84.5mg), diphenylphosphine (0.2mmol, 37.2mg) and reaction at room temperature for 1 hour, solvent spin-drying, and column chromatography to give compound P26 (57% yield, 49.8 mg). P26 is an unknown compound and the assay data is as follows: white solid (R) f 0.36,100% ethyl acetate). 1 H NMR(400MHz,CDCl 3 )δ7.85(dd,J＝13.8,7.1Hz,4H),7.63–7.55(m,2H),7.53–7.45(m,4H),2.40(dd,J＝7.5,1.7Hz,4H),2.26(p,J＝7.7Hz,2H),1.84–1.73(m,4H),1.64–1.56(m,4H),1.55–1.46(m,4H),1.21–1.09(m,4H). 13 C NMR(101MHz,CDCl 3 )δ180.71,133.09,133.06,132.63,132.52,128.69,128.55,127.89,126.65,45.92,45.80,37.26,32.55,25.15. 31 P NMR(162MHz,CDCl 3 )δ24.39.HRMS(ESI)m/z Calcd for C 26 H 34 N 2 O 2 P + [M+H] + :437.2352,found:437.2348.
Preparation of P27: in a glove box, ferrous chloride tetrahydrate (5 mol%, 2.0mg) was charged into an 8mL reaction flask, chloroform (0.5mL), 3- (styryl) -1,4, 2-dioxazol-5-one (0.5mmol, 2.5 equiv., 94.5mg), diphenylphosphine (0.2mmol, 37.2mg) were added in this order, and reaction was carried out at room temperature for 1After a short time, the solvent was dried by evaporation and column chromatography gave compound P27 (52% yield, 49.6 mg). P27 is an unknown compound and the assay data is as follows: white solid (R) f 0.36,100% ethyl acetate). 1 H NMR(400MHz,CDCl 3 )δ10.59(brs,1H),7.98(dd,J＝13.7,7.6Hz,4H),7.63(d,J＝15.6Hz,2H),7.59–7.51(m,2H),7.50–7.40(m,8H),7.37–7.29(m,6H),6.77(d,J＝15.7Hz,2H). 13 C NMR(101MHz,CDCl 3 )δ172.70,142.65,142.63,134.89,132.97,132.94,132.79,132.67,129.84,128.80,128.66,128.52,128.18,127.68,126.45,123.87,123.72. 31 P NMR(162MHz,CDCl 3 )δ25.51.HRMS(ESI)m/z Calcd for C 30 H 26 N 2 O 2 P + [M+H] + :477.1726,found:477.1725.
Preparation of P28: in a glove box, ferric chloride hexahydrate (5 mol%, 2.7mg) was charged into an 8mL reaction flask, and methylene chloride (0.5mL), 3- (2-phthalimidopropyl) -1,4, 2-dioxazol-5-one (0.5mmol, 2.5 equiv., 137mg), diphenylphosphine (0.2mmol, 37.2mg) were sequentially added, reacted at room temperature for 1 hour, the solvent was spin-dried, and column chromatography was performed to obtain compound P28 (95% yield, 130 mg). P28 is an unknown compound and the assay data is as follows: white solid (R) f 0.67,100% ethyl acetate). 1 H NMR(400MHz,CDCl 3 )δ9.29(brs,1H),7.80–7.72(m,4H),7.70–7.55(m,8H),7.42(t,J＝3.9Hz,2H),7.26–7.17(m,4H),4.81(q,J＝7.1Hz,2H),3.21(dd,J＝15.5,9.1Hz,2H),2.84(dd,J＝15.5,5.7Hz,2H),1.45(d,J＝6.9Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ167.97,133.76,133.55,132.39,132.36,132.14,132.03,131.80,131.77,128.12,127.98,127.03,125.80,122.97,122.88,44.26,42.39,18.70,18.62. 31 P NMR(162MHz,CDCl 3 )δ23.09.HRMS(ESI)m/z Calcd for C 36 H 32 N 4 O 6 P + [M+H] + :647.2054,found:647.2057.
Preparation of P29: in a glove box, ferrous chloride tetrahydrate (5 mol%, 2.0mg) was charged into an 8mL reaction flask, followed by addition of 1, 2-dichloroethane (0.5mL), 3-cyclohexyl-1, 4, 2-dioxazol-5-one (0.5mmol, 2.5 equiv., 84.5mg), diphenylphosphine (0.2mmol, 37.2mg) in that order, reaction at room temperature for 1 hour, spin-drying of the solvent, and column chromatography to give compound P29 (46% yield, 40.2 mg). P29 is an unknown compound and the assay data is as follows: white solid (R) f 0.64, petroleum ether: ethyl acetate 2: 1). 1 H NMR(400MHz,CDCl 3 )δ10.21(brs,1H),7.92–7.75(m,4H),7.63–7.53(m,2H),7.52–7.43(m,4H),2.32(tt,J＝11.7,3.7Hz,2H),2.03–1.90(m,4H),1.76(dt,J＝12.3,3.3Hz,4H),1.68–1.59(m,2H),1.48–1.36(m,4H),1.34–1.18(m,6H). 13 C NMR(101MHz,CDCl 3 )δ183.82,132.98,132.95,132.53,132.42,128.68,128.55,127.22,47.90,47.77,29.86,25.95,25.88,25.83,25.79. 31 P NMR(162MHz,CDCl 3 )δ23.93.HRMS(ESI)m/z Calcd for C 26 H 34 N 2 O 2 P + [M+H] + :437.2352,found:437.2354.
Preparation of P30: in a glove box, ferrous iodide (5 mol%, 3.1mg) was charged into an 8mL reaction flask, and 1, 2-dichloroethane (0.5mL), 3- (4-iodophenyl) -1,4, 2-dioxazol-5-one (0.5mmol, 2.5 equiv, 144.5mg), diphenylphosphine (0.2mmol, 37.2mg) were added in this order to react at room temperature for 2 hours, the solvent was spin-dried, and column chromatography was performed to obtain compound P30 (83% yield, 112.2 mg). P30 is an unknown compound and the assay data is as follows: white solid (R) f 0.5, petroleum ether: ethyl acetate 5: 1). 1 H NMR(400MHz,CDCl 3 )δ11.69(brs,1H),7.96(dd,J＝14.0,7.7Hz,4H),7.90–7.73(m,8H),7.64(dd,J＝8.4,6.4Hz,2H),7.59–7.48(m,4H). 13 C NMR(101MHz,CDCl 3 )δ172.53,137.74,133.48,133.45,132.79,132.68,130.51,128.90,128.76,127.81,126.53,100.01. 31 P NMR(162MHz,CDCl 3 )δ27.29.HRMS(ESI)m/z Calcd for C 26 H 20 I 2 N 2 O 2 P + [M+H] + :676.9346,found:676.9349.
Preparation of P31: in a glove box, ferrous chloride tetrahydrate (5 mol%, 2.0mg) was charged into an 8mL reaction flask, tetrachloroethane (0.5mL), 3-methyl-1, 4, 2-dioxazol-5-one (0.5mmol, 2.5 equiv, 50.5mg), and bis- (3, 5-dimethylphenyl) phosphine (0.2mmol, 48.4mg) were sequentially added, reacted at room temperature for 1 hour, and the solvent was spin-dried and column-chromatographed to give compound P31 (82% yield, 58.5 mg). P31 is an unknown compound and the assay data is as follows: white solid (R) f 0.2,100% ethyl acetate). 1 H NMR(400MHz,CDCl 3 )δ7.42(d,J＝14.1Hz,4H),7.20(s,2H),2.34(s,12H),2.16(d,J＝2.1Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ177.99,138.49,138.34,135.04,135.01,130.05,129.94,127.42,126.19,26.87,26.74,21.50,21.43. 31 P NMR(162MHz,CDCl 3 )δ23.86.HRMS(ESI)m/z Calcd for C 20 H 26 N 2 O 2 P + [M+H] + :357.1726,found:357.1727.
Preparation of P32: in a glove box, ferrous fluoride (5 mol%, 0.9mg) was added to an 8mL reaction flask, and 1, 2-dichloroethane (0.5mL), 3-methyl-1, 4, 2-dioxazol-5-one (0.5mmol, 2.5 equiv, 50.5mg), isopropylphenylphosphine (0.2mmol, 30.4mg) were added in this order to react at room temperature for 2 hours, and the solvent was spin-dried and column-chromatographed to obtain compound P32 (81% yield, 50.7 mg). P32 is an unknown compound and the assay data is as follows: white solid (R) f 0.3,100% ethyl acetate). 1 H NMR(400MHz,CDCl 3 )δ9.85(brs,1H),7.96–7.85(m,2H),7.61–7.52(m,1H),7.52–7.41(m,2H),3.23–3.09(m,1H),2.14(d,J＝1.9Hz,6H),1.15(dd,J＝18.8,7.1Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ178.60,132.93,132.90,131.91,131.81,128.74,128.61,127.60,126.51,26.75,26.62,25.01,24.16,14.66,14.63. 31 P NMR(162MHz,CDCl 3 )δ38.09.HRMS(ESI)m/z Calcd for C 16 H 30 N 2 O 2 P + [M+H] + :313.2039,found:313.2039.
Preparation of P33: in a glove box, iron fluoride (5 mol%, 1.1mg) was charged into an 8mL reaction flask, methylene chloride (0.5mL), 3-methyl-1, 4, 2-dioxazol-5-one (0.5mmol, 2.5 equiv, 50.5mg), dicyclohexylphosphine (0.2mmol, 39.6mg) were sequentially added, and the reaction was carried out at room temperature for 1 hour, followed by spin-drying the solvent and column chromatography to obtain compound P33 (67% yield, 35.8 mg). P33 is an unknown compound and the assay data is as follows: white solid (R) f 0.15, petroleum ether: ethyl acetate 2: 1). 1 H NMR(400MHz,CDCl 3 )δ9.88(brs,1H),2.46–2.31(m,2H),2.10(d,J＝1.8Hz,6H),1.90–1.78(m,8H),1.76–1.66(m,2H),1.58–1.41(m,4H),1.36–1.19(m,6H). 13 C NMR(101MHz,CDCl 3 )δ178.27,35.10,34.35,26.75,26.62,26.18,26.04,25.67,25.66,24.99,24.95. 31 P NMR(162MHz,CDCl 3 )δ50.86.HRMS(ESI)m/z Calcd for C 13 H 20 N 2 O 2 P + [M+H] + :267.1257,found:267.1257.
A process for preparing a phosphonamide having the general reaction formula:
preferably, when R is 2 ＝R 3 Is phenyl, R 1 The corresponding phosphonamide product P34 was obtained in 95% yield when taken together with methyl.
For the other compounds of the formula I according to the invention, it is also possible to prepare phosphonamides by the methods described above, as would be expected by the person skilled in the art.
Preparation of P34: ferrous chloride tetrahydrate (5 mol%, 4.0mg) was charged into an 8mL reaction flask, 1, 2-dichloroethane (1mL), diphenylphosphine (2 eq, 148.8mg), 3-methyl-1, 4, 2-dioxazol-5-one (0.4mmol,40.4mg) were added, the reaction was carried out at room temperature for 1 hour, and 30% H was added 2 O 2 To yield compound P34 (95% yield, 98.4mg), by reaction for 10 minutes, spin-drying the solvent, and column chromatography. Compound P34 was an unknown compound and the monitoring data are as follows. White solid (R) f 0.17,100% ethyl acetate). 1 H NMR(400MHz,CDCl 3 )δ9.39(s,1H),7.89–7.44(m,4H),7.56(td,J＝7.3,1.6Hz,2H),7.51–7.39(m,4H),2.13(s,3H). 13 C NMR(101MHz,CDCl 3 )δ173.40,132.67,132.64,131.97,131.86,131.52,130.25,128.65,128.51,24.55,24.50. 31 P NMR(162MHz,CDCl 3 )δ27.06.HRMS(ESI)m/z Calcd for C 14 H 14 NNaO 2 P + [M+Na] + :282.0654,found:282.0655.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A method for preparing a compound containing a P-N bond is characterized in that a phosphine-containing compound and 3-substituted-1, 4, 2-dioxazole-5-ketone are used as raw materials and react under the condition of an iron catalyst to generate a compound containing the P-N bond in a formula I;
the structural formula of the 3-substituted-1, 4, 2-dioxazole-5-ketone is as follows:
wherein R is 1 Selected from alkyl, alkyl substituted by halogen, alkenyl or hetero atom, cyclic hydrocarbon or aryl,
The structural formula of the phosphine-containing compound is as follows:
wherein R is 2 、R 3 The same or different, independently selected from at least one of alkyl, cyclic hydrocarbon or aryl; or
Is selected from
The compound of formula I has the following general structural formula:
the iron catalyst is more than one of a halogenated iron catalyst, ferrous chloride or ferrous chloride tetrahydrate;
the concentration of the 3-substituted-1, 4, 2-dioxazole-5-one is 0.4-4 mol/L; the molar ratio of the phosphine-containing compound to 3-substituted-1, 4, 2-dioxazole-5-one is 1-2: 1; the mol ratio of the iron catalyst to the 3-substituted-1, 4, 2-dioxazole-5-ketone is 0.1-5 percent to 1.
2. The method for producing a compound having a P-N bond according to claim 1,
the R is 1 Can be selected from any one of the following groups:
3. the method for preparing a compound having a P-N bond according to claim 1, wherein the iron catalyst is: one or more of ferric chloride, ferric chloride hexahydrate, ferrous bromide, ferric bromide, ferrous iodide, ferrous fluoride or ferric fluoride;
the solvent used in the reaction is more than one of 1, 2-dichloroethane, dichloromethane, trichloromethane, 1,2, 2-tetrachloroethane, toluene, chlorobenzene, tetrahydrofuran, acetonitrile, diethyl ether or ethyl acetate;
the reaction temperature is room temperature, and the reaction time is 10 minutes to 10 hours.
4. The method for preparing the compound containing the P-N bond, as claimed in claim 1, characterized in that, adding borane complex into the compound of the formula I to obtain the compound of the formula II and/or the compound of the formula IV;
the compound of formula II and the compound of formula IV have the following structural general formulas:
the borane complex is one of borane tetrahydrofuran complex and borane dimethyl sulfide complex; the molar ratio of the borane complex to the 3-substituted-1, 4, 2-dioxazole-5-one is 3-5: 1, correspondingly obtaining a compound shown in the formula IV, wherein the molar ratio of the borane complex to the 3-substituted-1, 4, 2-dioxazole-5-ketone is 1-2: 1, corresponding to the compound of formula II.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110631151.7A CN113321683B (en) | 2021-06-07 | 2021-06-07 | Compounds containing P-N bonds and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110631151.7A CN113321683B (en) | 2021-06-07 | 2021-06-07 | Compounds containing P-N bonds and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113321683A CN113321683A (en) | 2021-08-31 |
| CN113321683B true CN113321683B (en) | 2022-08-26 |
Family
ID=77421138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110631151.7A Active CN113321683B (en) | 2021-06-07 | 2021-06-07 | Compounds containing P-N bonds and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113321683B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3136801A (en) * | 1961-10-12 | 1964-06-09 | Lubrizol Corp | Phosphorus-containing carbamic composition |
| JP2003535860A (en) * | 2000-06-05 | 2003-12-02 | ドン・ア・ファーム・カンパニー・リミテッド | Novel oxazolidinone derivative and method for producing the same |
| CN107827907A (en) * | 2017-11-10 | 2018-03-23 | 浙江普洛得邦制药有限公司 | The preparation method and application of Yi Zhong oxazolidone pharmaceutical intermediates |
| CN109354583B (en) * | 2018-12-21 | 2020-07-17 | 北京工业大学 | Chiral 3, 4-dihydro-2 (1H) -quinolinone compound and preparation method thereof |
| CN109762018A (en) * | 2019-01-17 | 2019-05-17 | 大连理工大学 | A kind of preparation method of the phosphorus nitrence compound of ruthenium catalysis |
| CN109762017B (en) * | 2019-01-17 | 2021-06-18 | 大连理工大学 | Preparation method of iron-catalyzed phosphazene compound |
| CN109970789B (en) * | 2019-04-25 | 2021-05-07 | 大连理工大学 | Preparation method of triarylphosphine compound |
| CN112142792A (en) * | 2020-09-16 | 2020-12-29 | 大连理工大学 | Novel method for constructing nitrogen-phosphorus double bonds through visible light catalysis |
-
2021
- 2021-06-07 CN CN202110631151.7A patent/CN113321683B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113321683A (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Catalytic addition of alkyne C–H, amine N–H, and phosphine P–H bonds to carbodiimides: an efficient route to propiolamidines, guanidines, and phosphaguanidines | |
| Sasai et al. | The first heterobimetallic multifunctional asymmetric catalyst | |
| CN101990543B (en) | Method for manufacturing ruthenium carbene complexes | |
| Kireenko et al. | Palladium complexes with stabilized germylene and stannylene ligands | |
| Zhao | A novel 3D MOF with rich lewis basic sites as a base catalysis toward knoevenagel condensation reaction | |
| CN104812765A (en) | Method for the synthesis of alpha-aminoalkylenephosphonic acid | |
| US20110172432A1 (en) | Method for the synthesis of heterogeneous palladium catalysts, catalysts obtained and use of same | |
| WO2018050901A1 (en) | A versatile process for the preparation of acylphosphines | |
| CN113321683B (en) | Compounds containing P-N bonds and preparation method thereof | |
| Heinze et al. | Cobalt‐Catalyzed Selective Oxidation of the Tritertiary Phosphane Triphos with Molecular Oxygen | |
| Cui et al. | The synthesis and reactivity of 16-electron half-sandwich iridium complexes bearing a carboranylthioamide ligand | |
| Morgalyuk et al. | Ambident Reactivity of Chloro (dialkylamino)(diphenylphosphinoyl) methanes | |
| Takemura et al. | Interconversion between ladder-type octanuclear and linear tetranuclear copper (I) complexes supported by tetraphosphine ligands | |
| Biricik et al. | New bis (diphenylphosphino) aniline derivatives: Synthesis and spectroscopic characterization | |
| Zhou et al. | A facile approach to C-functionalized β-ketoimine compounds via terminal alkylation of a tetralithiated intermediate | |
| Schull et al. | Synthesis of symmetrical triarylphosphines from aryl fluorides and red phosphorus: scope and limitations | |
| CN110105230A (en) | A kind of method of palladium/imidazole salts catalysis nitro-aromatic and aminated compounds synthesis aromatic amine compound | |
| Matt et al. | Reactivity of phosphine-phosphinite complexes. synthesis and crystal structure of [{Ph2PCH C (O) Ph} Pd (μ-Ph2PO)] 2 | |
| JPH09241276A (en) | Production of alkenylphosphine oxide compound | |
| Lin et al. | Tandem addition of nucleophilic and electrophilic reagents to vinyl phosphinates: The stereoselective formation of organophosphorus compounds with congested tertiary carbons | |
| Chen et al. | Metal-free visible-light-induced phosphorylation of unactivated alkyl iodides with white phosphorus as the P-atom source | |
| CN100412079C (en) | Process for production of phosphine-borane complexes | |
| CN108654695B (en) | Indole [3,2-a ] oxazolidine-labeled ruthenium carbene catalyst, and preparation method and application thereof | |
| Langer et al. | An iridium-mediated C–H activation/CO 2-carboxylation reaction of 1, 1-bisdiphenylphosphinomethane | |
| US6455704B1 (en) | Process for the preparation of base-free carbazolide anions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |