CN109096082B - Method for synthesizing alpha-iodo-cyclopentenone compound - Google Patents
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- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
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- C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
- C07C311/21—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
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- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
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- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
Abstract
The invention discloses a method for synthesizing alpha-iodo-cyclopentenone compounds, which comprises the steps of adding enyne ester and gold (I) hexafluoroantimonate into methyl tert-butyl ether solution, stirring for 1 hour, confirming that all raw materials completely react through TLC, and then adding N-iodo-succinimide. The invention provides a method for synthesizing alpha-iodo-cyclopentenone compounds from acyclic enyne ester compounds. The whole reaction is carried out at normal temperature and normal pressure, and has the advantages of simple and convenient operation, mild conditions, good substrate functional group compatibility, high product yield, easy separation of the catalyst and the product and the like. The developed alpha-iodo-cyclopentenone compound has high reaction activity and can be used as an important organic intermediate to be applied to the fields of medicines, pesticides, synthesis of natural products and the like.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for synthesizing alpha-iodo-cyclopentenone.
Background
The halogenated carbonyl compound is an important intermediate in the fields of organic synthesis, biomedicine, pharmacy and the like. The most common of these are the α -halo ketones, and most have potential biological activity. For example, George Sakoulas et al report a novel natural product, Merochlorin A, which has in vitro activity against multidrug gram-positive bacteria and has a completely different backbone structure from other antibacterial agents. The introduction of halogen atoms will provide some novel methods for further chemical transformation of functional molecules including natural products, drugs, etc.
However, the known synthesis method of alpha-iodoketone is only limited to acyclic alpha-iodoketone, and efficient synthesis of alpha-iodocyclic ketene from acyclic precursor compounds is not reported. The invention provides a preparation method for synthesizing alpha-iodo-cyclopentenone, which has the advantages of mild condition, simple and convenient operation, high yield and good substrate applicability, and provides a new way for synthesizing alpha-iodo-cyclopentenone and complex natural products.
Disclosure of Invention
The invention aims to solve the problems and provide a methodGood compatibility of substrate functional group and high product yieldThe process for synthesizing alpha-iodocyclopentenone.
In order to solve the technical problems, the invention provides the following technical scheme: the alpha-iodo-cyclopentenone compound has the structural general formula:
in the formula, R1、R2Are independent groups, and the carbon number is 1-16;
R1is a substituent group and comprises any one of phenyl, naphthyl, halogenated phenyl and cycloalkyl;
R2the substituent group comprises one or a combination of several of methyl, chain alkyl, cycloalkyl, carbonyl, ester group, benzenesulfonyl, phenyl and nitrogen-containing heterocyclic groups.
The method for synthesizing the alpha-iodo-cyclopentenone compound comprises the following steps of: adding methyl tert-butyl ether, enyne ester and gold (I) hexafluoroantimonate (acetonitrile) [ (2-biphenyl) di-tert-butylphosphine ] sequentially, stirring for 1 hour, confirming that all raw materials completely react by TLC, adding N-iodosuccinimide, stirring for 2 hours at normal temperature and normal pressure, performing rotary evaporation and concentration on reaction liquid, and performing silica gel column chromatography to obtain a target product alpha-iodocyclopentenone.
Further, the enyne ester comprises the enyne ester compound shown in the specification,
in the formula, R1、R2Same as R1、R2And the correspondence is consistent.
Further, the concentration of the enyne ester in the methyl tert-butyl ether is 0.1 mol/L.
Furthermore, the mol ratio of the enyne ester to the gold (I) hexafluoroantimonate is 1: 0.02.
Further, the mol ratio of the enyne ester to the N-iodosuccinimide is 1: 2.
Further, the rotary evaporation speed is 150-300 rpm, the temperature is 35-45 ℃, the vacuum degree is 0.05-0.09 Mpa, and the treatment time is 5-15 min.
Furthermore, the silica gel column chromatography adopts 200-300 mesh column chromatography silica gel, and the eluent is ethyl acetate and petroleum ether which are 1-30: 100.
Has the advantages that: the whole reaction is carried out at normal temperature and normal pressure, and the method has the advantages of simple operation, mild conditions, good compatibility of substrate functional groups, high product yield, easy separation of catalyst and product and the like. The developed alpha-iodo-cyclopentenone compound has high reaction activity and can be used as an important organic intermediate to be applied to the fields of medicines, pesticides, synthesis of natural products and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a nuclear magnetic hydrogen spectrum of Compound 2 a;
FIG. 2 is a nuclear magnetic carbon spectrum of compound 2a, and FIGS. 1 and 2 show that compound 2a has a correct structure;
FIG. 3 is a nuclear magnetic hydrogen spectrum of Compound 2 b;
FIG. 4 is a nuclear magnetic carbon spectrum of Compound 2b, and FIGS. 3 and 4 show that Compound 2b has the correct structure;
FIG. 5 is a nuclear magnetic hydrogen spectrum of Compound 2 c;
FIG. 6 is a nuclear magnetic carbon spectrum of Compound 2c, and FIGS. 5 and 6 show that Compound 2c has the correct structure;
FIG. 7 is a nuclear magnetic hydrogen spectrum of Compound 2 d;
fig. 8 is a nuclear magnetic carbon spectrum of compound 2d, and fig. 7 and 8 show that compound 2d has a correct structure;
FIG. 9 is a nuclear magnetic hydrogen spectrum of Compound 2 e;
fig. 10 is a nuclear magnetic carbon spectrum of compound 2e, and fig. 9 and 10 show that compound 2e has a correct structure;
FIG. 11 is a nuclear magnetic hydrogen spectrum of Compound 2 f;
fig. 12 is a nuclear magnetic carbon spectrum of compound 2f, and fig. 11 and 12 show that compound 2f has a correct structure;
FIG. 13 is a nuclear magnetic hydrogen spectrum of Compound 2 g;
FIG. 14 is the nuclear magnetic carbon spectrum of compound 2g, and FIGS. 13 and 14 show that compound 2g has the correct structure;
FIG. 15 is a nuclear magnetic hydrogen spectrum of Compound 2 h;
fig. 16 is the nuclear magnetic carbon spectrum of compound 2h, and fig. 15 and 16 show that compound 2h has the correct structure.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Example 1
A25 mL round-bottomed flask was charged with 5mL of methyl t-butyl ether, eneyne 1a (107.2mg, 0.5mmol), and gold (I) hexafluoroantimonate (acetonitrile) [ (2-biphenyl) di-t-butylphosphine ] (7.8mg, 0.01mmol) in this order, and after stirring for 1 hour, it was confirmed by TLC that all the starting materials had reacted, and N-iodosuccinimide (225mg, 1mmol) was further added. The mixture was stirred at 500rpm for 2 hours at normal temperature and pressure. And performing rotary evaporation with Heidolph rotary evaporator at 150rpm, 42 deg.C, vacuum degree of 0.06Mpa, and treatment time of 10 min. And performing 200-300-mesh silica gel column chromatography, wherein the eluent is ethyl acetate and petroleum ether which are 3: 100, and separating to obtain the target product 2a (136.7mg, 0.46mmol, the yield is 93%, and the high purity of the product can be reflected in the aspects of nuclear magnetic spectrum appearance, signals, noise and the like).
1H NMR(600MHz，CDCl3)：δ7.62-7.60(m，2H)，7.51-7.44(m，3H)，6.60(t，1H，J＝1.7Hz)，3.86(dd，1H，J＝19.1，1.5Hz)，3.47(dd，1H，J＝19.1，2.0Hz)，2.02(s，3H)；13C NMR(150MHz，CDCl3)：δ204.8，167.2，133.1，131.9，129.1，127.0，121.9，51.2，37.7，30.6.
Example 2
A25 mL round-bottomed flask was charged with 5mL of methyl t-butyl ether, enyne 1b (151mg, 0.5mmol), and gold (I) hexafluoroantimonate (acetonitrile) [ (2-biphenyl) di-t-butylphosphine ] (7.8mg, 0.01mmol) in this order, and after stirring for 1 hour, it was confirmed by TLC that all the starting materials had reacted, and N-iodosuccinimide (225mg, 1mmol) was further added. The mixture was stirred at 500rpm for 3 hours at normal temperature and pressure. And performing rotary evaporation with Heidolph rotary evaporator at 150rpm, 42 deg.C, vacuum degree of 0.06Mpa, and treatment time of 10 min. And performing 200-300 mesh silica gel column chromatography, wherein an eluent is ethyl acetate: petroleum ether is 5: 100, separating to obtain a target product 2b (176.7mg, 0.46mmol, the yield is 92%, and the product purity can be reflected in the aspects of nuclear magnetic spectrum appearance, signals, noise and the like).
1H NMR(600MHz，CDCl3)：δ7.60(d，2H，J＝7.3Hz)，7.50-7.43(m，3H)，6.59(s，1H)，4.08(t，2H，J＝6.3Hz)，3.69(d，1H，J＝19.2Hz)，3.46(dd，1H，J＝19.2，1.8Hz)，2.20-2.15(m，1H)，2.01(s，3H)，1.94-1.88(m，1H)，1.74-1.63(m，2H).
13C NMR(150MHz，CDCl3)：δ204.2，171.0，167.7，132.9，132.0，129.2，127.0，122.5，63.6，48.3，44.6，37.9，27.5，21.0.
Example 3
A25 mL round-bottomed flask was charged with 5mL of methyl t-butyl ether, eneyne 1c (243.8mg, 0.5mmol), and gold (I) hexafluoroantimonate (acetonitrile) [ (2-biphenyl) di-t-butylphosphine ] in this order (7.8mg, 0.01mmol), and after stirring for 1 hour, it was confirmed by TLC that all the starting material had reacted, and N-iodosuccinimide (225mg, 1mmol) was further added. The mixture was stirred at 500rpm for 2 hours at normal temperature and pressure. And performing rotary evaporation with Heidolph rotary evaporator at 150rpm, 42 deg.C, vacuum degree of 0.06Mpa, and treatment time of 10 min. And performing 200-300-mesh silica gel column chromatography, wherein the eluent is ethyl acetate and petroleum ether at a ratio of 20: 100, and separating to obtain the target product 2c (245.7mg, 0.43mmol, the yield is 86%, and the product purity can be reflected in aspects of nuclear magnetic spectrum appearance, signals, noise and the like).
1H NMR(600MHz，CDCl3)：δ7.57-7.56(m，2H)，7.50-7.49(m，1H)，7.47-7.43(m，4H)，7.30-7.28(m，3H)，7.23(d，2H，J＝8.0Hz)，7.05-7.03(m，2H)，6.55(t，1H，J＝1.6Hz)，3.63-3.56(m，3H)，3.34(dd，1H，J＝19.1，1.9Hz)，2.41(s，3H)，2.16(t，1H，J＝10.3Hz)，1.75-1.69(m，2H)，1.58-1.54(m，1H).
13C NMR(150MHz，CDCl3)：δ204.1，167.7，143.5，139.0，134.9，132.9，131.9，129.4，129.1，129.1，128.7，128.0，127.7，127.0，122.4，49.9，48.5，44.7，38.2，27.1，21.6.
Example 4
A25 mL round-bottomed flask was charged with 5mL of methyl t-butyl ether, eneyne 1d (141.2mg, 0.5mmol), and gold (I) hexafluoroantimonate (acetonitrile) [ (2-biphenyl) di-t-butylphosphine ] (7.8mg, 0.01mmol) in this order, and after stirring for 1 hour, it was confirmed by TLC that all the starting materials had reacted, and N-iodosuccinimide (225mg, 1mmol) was further added. The mixture was stirred at 500rpm for 2 hours at normal temperature and pressure. And performing rotary evaporation with Heidolph rotary evaporator at 150rpm, 42 deg.C, vacuum degree of 0.06Mpa, and treatment time of 10 min. And performing 200-300-mesh silica gel column chromatography, wherein the eluent is ethyl acetate and petroleum ether which are 3: 100, and separating to obtain the target product 2d (162.9mg, 0.45mmol, the yield is 89%, and the high purity of the product can be reflected in the aspects of nuclear magnetic spectrum appearance, signals, noise and the like).
1H NMR(600MHz，CDCl3)：δ7.64-7.62(m，2H)，7.51-7.44(m，3H)，6.63(t，1H，J＝1.7Hz)，3.55(qd，2H，J＝19.4，1.9Hz)，2.36(d，1H，J＝12.8Hz)，2.05-2.00(m，1H)，1.89(d，1H，J＝13.6Hz)，1.65(dd，3H，J＝10.4，1.4Hz)，1.37-1.11(m，4H)，0.89(qd，1H，J＝11.9，2.9Hz).
13C NMR(150MHz，CDCl3)：δ204.9，168.0，133.2，131.8，129.1，127.0，123.4，54.2，46.4，45.0，31.7，27.2，26.6，26.2，25.6.
Example 5
A25 mL round-bottomed flask was charged with 5mL of methyl t-butyl ether, eneyne 1e (124.4mg, 0.5mmol), and gold (I) hexafluoroantimonate (acetonitrile) [ (2-biphenyl) di-t-butylphosphine ] (7.8mg, 0.01mmol) in this order, and after stirring for 1 hour, it was confirmed by TLC that all the starting materials had reacted, and N-iodosuccinimide (225mg, 1mmol) was further added. The mixture was stirred at 500rpm for 2 hours at normal temperature and pressure. And performing rotary evaporation with Heidolph rotary evaporator at 150rpm, 42 deg.C, vacuum degree of 0.06Mpa, and treatment time of 10 min. And performing 200-300-mesh silica gel column chromatography, wherein an eluent is ethyl acetate and petroleum ether which are 3: 100, and separating to obtain a target product 2e (138.1mg, 0.42mmol, the yield is 83%, and the high purity of the product can be reflected in aspects of nuclear magnetic spectrum appearance, signals, noise and the like).
1H NMR(600MHz，CDCl3)：δ7.54-7.52(m，2H)，7.43-7.42(m，2H)，6.54(t，1H，J＝1.7Hz)，3.79(dd，1H，J＝19.1，1.4Hz)，3.41(dd，1H，J＝19.1，2.0Hz)，1.99(s，3H).13C NMR(150MHz，CDCl3)：δ204.5，165.6，138.0，131.6，129.4，128.2，122.3，51.1，37.3，30.5.
Example 6
A25 mL round-bottomed flask was charged with 5mL of methyl t-butyl ether, eneyne 1f (132.2mg, 0.5mmol), and gold (I) hexafluoroantimonate (acetonitrile) [ (2-biphenyl) di-t-butylphosphine ] (7.8mg, 0.01mmol) in this order, and after stirring for 1 hour, it was confirmed by TLC that all the starting materials had reacted, and N-iodosuccinimide (225mg, 1mmol) was further added. The mixture was stirred at 500rpm for 2 hours at normal temperature and pressure. And performing rotary evaporation with Heidolph rotary evaporator at 150rpm, 42 deg.C, vacuum degree of 0.06Mpa, and treatment time of 10 min. And performing 200-300-mesh silica gel column chromatography, wherein an eluent is ethyl acetate and petroleum ether which are 5: 100, and separating to obtain a target product 2f (156.7mg, 0.45mmol, the yield is 90%, and the high purity of the product can be reflected in the aspects of nuclear magnetic spectrum appearance, signals, noise and the like).
1H NMR(600MHz，CDCl3)：δ8.02(s，1H)，7.91-7.86(m，3H)，7.71(dd，1H，J＝8.6，1.8Hz)，7.60-7.54(m，2H)，6.69(t，1H，J＝1.7Hz)，3.99(dd，1H，J＝18.9，1.4Hz)，3.57(dd，1H，J＝18.9，2.0Hz)，2.05(s，3H).
13C NMR(150MHz，CDCl3)：δ204.8，166.9，134.8，132.9，130.4，129.0，128.9，128.2，127.9，127.3，127.1，123.8，122.2，51.2，37.8，30.7.
Example 7
A25 mL round-bottomed flask was charged with 5mL of methyl t-butyl ether, 1g (128.2mg, 0.5mmol) of enyne, and (7.8mg, 0.01mmol) of gold (I) hexafluoroantimonate [ (2-biphenyl) di-t-butylphosphine ], in this order, and after stirring for 1 hour, it was confirmed by TLC that all the starting materials had reacted, and N-iodosuccinimide (225mg, 1mmol) was further added. The mixture was stirred at 500rpm for 2 hours at normal temperature and pressure. And performing rotary evaporation with Heidolph rotary evaporator at 150rpm, 42 deg.C, vacuum degree of 0.06Mpa, and treatment time of 10 min. And performing 200-300-mesh silica gel column chromatography, wherein an eluent is ethyl acetate and petroleum ether in a ratio of 5: 100, and separating to obtain 2g of a target product (98.7mg, 0.29mmol, the yield is 58%, and the product purity can be reflected in aspects of nuclear magnetic spectrum appearance, signals, noise and the like).
1H NMR(600MHz，C6D6)：δ7.18-7.15(m，2H)，7.09(t，1H，J＝7.4Hz)，6.97(d，2H，J＝7.2Hz)，5.65(s，1H)，2.79(d，1H，J＝19.4Hz)，2.26(t，2H，J＝7.5Hz)，2.13(dd，1H，J＝20.3，0.8Hz)，1.66(s，3H)，1.62-1.59(m，2H)，1.38-1.33(m，2H)；
13C NMR(150MHz，C6D6)：δ203.3，173.6，141.2，128.4(d，2C，J＝10.3Hz)，126.1，123.8，53.0，38.0，35.1，31.8，29.8，27.8.
Example 8
A25 mL round-bottomed flask was charged with 5mL of methyl t-butyl ether, eneyne 1h (127.2mg, 0.5mmol), and gold (I) hexafluoroantimonate (acetonitrile) [ (2-biphenyl) di-t-butylphosphine ] in this order (7.8mg, 0.01mmol), and after stirring for 1 hour, it was confirmed by TLC that all the starting material had reacted, and N-iodosuccinimide (225mg, 1mmol) was further added. The mixture was stirred at 500rpm for 2 hours at normal temperature and pressure. And performing rotary evaporation with Heidolph rotary evaporator at 150rpm, 42 deg.C, vacuum degree of 0.06Mpa, and treatment time of 10 min. And performing 200-300-mesh silica gel column chromatography, wherein an eluent is ethyl acetate and petroleum ether which are 3: 100, and separating to obtain a target product for 2h (93.0mg, 0.28mmol, the yield is 55%, and the product purity can be reflected in the aspects of nuclear magnetic spectrum appearance, signals, noise and the like).
1H NMR(600MHz，CDCl3)：δ7.61-7.60(m，2H)，7.48-7.46(m，3H)，6.50(s，1H)，4.01(dd，1H，J＝9.4，6.5Hz)，2.61-2.57(m，1H)，2.38-2.33(m，1H)，2.14-2.09(m，1H)，1.62-1.51(m，3H)，1.32-1.16(m，2H).
13C NMR(150MHz，CDCl3)：δ203.9，173.8，132.7，131.3，129.1，127.3，121.8，54.0，48.1，36.0，30.7，23.3，20.5.
Therefore, the invention provides a method for synthesizing alpha-iodo-cyclopentenone compounds from acyclic enyne ester compounds. The whole reaction is carried out at normal temperature and normal pressure, and has the advantages of simple and convenient operation, mild conditions, good substrate functional group compatibility, high product yield, easy separation of the catalyst and the product and the like. The developed alpha-iodo-cyclopentenone compound has high reaction activity and can be used as an important organic intermediate to be applied to the fields of medicines, pesticides, synthesis of natural products and the like.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (5)
1. A method for synthesizing alpha-iodo-cyclopentenone compounds is characterized by comprising the following steps: sequentially adding methyl tert-butyl ether, enyne ester and (acetonitrile) [ (2-biphenyl) di-tert-butylphosphine ] gold (I) hexafluoroantimonate, stirring for 1 hour, confirming that all raw materials completely react through TLC, adding N-iodosuccinimide, stirring for 2 hours at normal temperature and normal pressure, performing rotary evaporation and concentration on reaction liquid, and performing silica gel column chromatography to obtain a target product alpha-iodocyclopentenone;
the enyne ester comprises the following enyne ester compounds,
The concentration of the enyne ester in the methyl tert-butyl ether is 0.1 mol/L;
the structural general formula of the alpha-iodo-cyclopentenone compound is as follows:
In the formula, R1、R2Are independent groups, and the carbon number is 1-16;
R1is any one of phenyl, naphthyl, halogenated phenyl and cycloalkyl;
R2is one or a combination of more of chain alkyl, cycloalkyl, carbonyl, ester group, benzenesulfonyl, phenyl and nitrogen-containing heterocyclic groups.
2. The method of claim 1, wherein the α -iodocyclopentenone compound is selected from the group consisting of: the mol ratio of the enyne ester to the gold (I) hexafluoroantimonate is 1: 0.02.
3. The method of claim 1, wherein the α -iodocyclopentenone compound is selected from the group consisting of: the mol ratio of the enyne ester to the N-iodosuccinimide is 1: 2.
4. The method of claim 1, wherein the α -iodocyclopentenone compound is selected from the group consisting of: the rotary evaporation speed is 150-300 rpm, the temperature is 35-45 ℃, the vacuum degree is 0.05-0.09 Mpa, and the treatment time is 5-15 min.
5. The method of claim 1, wherein the α -iodocyclopentenone compound is selected from the group consisting of: the silica gel column chromatography adopts 200-300 mesh column chromatography silica gel, and the eluent is ethyl acetate and petroleum ether which are 1-30: 100.
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