CN110054553B - Method for synthesizing optically active ketone compound by asymmetric conjugate addition reaction of organic boric acid and alpha, beta-unsaturated ketone - Google Patents
Method for synthesizing optically active ketone compound by asymmetric conjugate addition reaction of organic boric acid and alpha, beta-unsaturated ketone Download PDFInfo
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Abstract
A method for synthesizing optically active ketone compounds by asymmetric conjugate addition reaction of organic boric acid and alpha, beta-unsaturated ketone belongs to the technical field of asymmetric synthesis in organic chemistry, and the reaction equation is as follows:
the method comprises the following specific steps: alpha, beta-unsaturated ketone 1 and organic boric acid 2 are taken as raw materials, and ketone compounds are obtained by asymmetric conjugate addition reaction in the presence of chiral tetraphenylocyclooctatetraene compounds as catalysts, molecular sieves and magnesium tert-butoxide additives, wherein R is1= phenyl, substituted phenyl, methyl; r2= phenyl, substituted phenyl, 2-thienyl, 2-furyl, 1-naphthyl, 2-naphthyl, ester group, R3= styryl, 2-furyl, 2-benzofuryl, n-octenyl. The invention has the advantages that: the method has the advantages of easily obtained reaction raw materials, novel catalyst structure, high catalytic efficiency, mild reaction conditions and simple post-treatment, and the ketone compound with high optical activity is obtained.
Description
Technical Field
The invention belongs to the technical field of asymmetric synthesis in organic chemistry, and particularly relates to a method for synthesizing an optically active ketone compound with high yield and enantioselectivity by catalyzing asymmetric conjugate addition reaction of organic boric acid and alpha, beta-unsaturated ketone by a chiral tetraphenylcyclooctyltetraene compound.
Background
The asymmetric conjugate addition reaction of an organic boride and an alpha, beta-unsaturated carbonyl compound is one of important synthetic methods for constructing a C-C bond (Molecules2018,23,2317.). Organic borides (alkyl boric acid, organic borate and organic borate) play an important role in modern organic synthesis due to the advantages of low toxicity, low price, easy availability, good stability, good functional group tolerance and the like, and small organic molecules catalyze the asymmetric conjugate addition reaction of the organic borides and alpha, beta-unsaturated carbonyl compounds ((a) org.Lett.2009,11,2425, (b) J.Am.chem.Soc.2007,129,15438, (c) J.Am.chem.Soc.2012,134,19965, (d) J.Am.chem.Soc.2005,127,3244, (e) Angew.chem.Int.Ed.2015.2015, 54,9931, (f) chem.Commun.2010,46,7799) have many advantages, such as low toxicity of the catalyst, easiness in preparation, low price, good stability, simplicity in operation, no metal residue after reaction and the like.
So far, the chiral catalysts used in the reaction are few, and organic borate which are not stable are mostly needed to be used, and reports of directly using the organic boric acid which is simple, easy to obtain and relatively stable are few. Therefore, the development of a high-efficiency transition metal-free catalytic system realizes the asymmetric conjugate addition reaction of the organic boric acid and the alpha, beta-unsaturated ketone to obtain a series of optically active ketone compounds, and has important research significance.
Disclosure of Invention
The invention aims to provide a method for synthesizing an optically active ketone compound by asymmetric conjugate addition reaction of organic boric acid and alpha, beta-unsaturated ketone.
Based on the purposes, the invention adopts organic boric acid and alpha, beta-unsaturated ketone as raw materials, and synthesizes the optically active ketone compound in one step with high yield and enantioselectivity through asymmetric conjugate addition reaction under the condition that a chiral tetraphenylcyclooctyltetraene compound is used as a catalyst and a molecular sieve and a tert-butyl alcohol magnesium additive.
The reaction equation is as follows:
wherein: r1Selected from Ph, 4-CH3OC6H4、4-BrC6H4、Me；R2Selected from Ph, 4-CH3OC6H4、4-FC6H4、4-ClC6H4、4-BrC6H4、2-BrC6H4、4-CF3C6H4、4-NO2C6H42-thienyl, 2-furyl, 1-naphthyl, 2-naphthyl or CO2Et；R3Is selected from
Further, in the above technical scheme, the chiral catalyst is selected from (S, S) -1,8,9, 16-tetrahydroxytetrabenzocyclooctatetraene ((S, S) -THTP), (S) -1, 16-dihydroxytetrabenzocyclooctatetraene ((S) -DHTP), (S) -2, 15-dibromo-1, 16-dihydroxytetrabenzocyclooctatetraene ((S) -2, 15-Br)2-DHTP), and (S) -2, 15-diphenyl-1, 16-dihydroxybenzocyclooctatetraene ((S) -2, 15-Ph)2-DHTP). Synthesis of chiral tetrabenzocyclooctatetraene catalyst was synthesized according to the reference (j.org.chem.2019,84,120.). The catalyst respectively corresponds to the following specific structures:
further, in the above technical scheme, the molar ratio of the α, β -unsaturated ketone 1, the organic boric acid 2, the catalyst, and the magnesium tert-butoxide is 1:1.2:0.05:0.05, and the amount of the molecular sieve in each 0.1mmol of the α, β -unsaturated ketone 1 is 100 mg.
Further, in the above technical solution, the reaction solvent is one of toluene, dichloromethane, tetrahydrofuran, methyl tert-butyl ether (MTBE), trifluorotoluene, o-xylene (o-xylene), 1, 2-Dichloroethane (DCE), diisopropyl ether, 1, 4-dioxane, and acetonitrile.
Further, in the above technical scheme, the reaction temperature is 0 to 25 ℃, preferably 25 ℃.
Further, in the above technical scheme, the whole reaction process needs to be carried out under nitrogen or argon atmosphere, preferably nitrogen.
The invention has the beneficial effects that:
the invention has the advantages of easily obtained reaction raw materials, mild reaction conditions, simple post-treatment, recyclable and reusable catalyst, and good to excellent product yield and enantioselectivity.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited thereto.
Example 1:
aunless otherwise stated, trans-chalcone 1a (0.1mmol), trans-2-phenylvinylboronic acid 2a (0.12mmol), catalyst (0.01mmol), Mg (O)tBu)2(0.01mmol),
Molecular sieves (100mg), and 1.0mL of anhydrous solvent in N2Stirring under an atmosphere.bIsolated yield.cThe ee value was obtained by chiral column HPLC analysis.dAt 0 ℃.eCat1(0.005mmol,5mol％),Mg(OtBu)2(0.005mmol,5mol％).fCat1(0.002mmol,2mol％),Mg(OtBu)2(0.002mmol,2mol％).
In the screening process of the reaction conditions, the influence of different solvents on the reaction is firstly examined (entries1-10), and finally, methyl tert-butyl ether is used as the solvent. Subsequently, the influence of different chiral catalysts on the reaction was examined (entries11-13), and Cat1 was finally determined as the optimal catalyst. The influence of temperature and catalyst amount on the reaction (entries14-16) was also examined, and finally the reaction temperature was selected to be 25 ℃ and the catalyst amount was 5 mol%.
Examination of reaction conditions (taking entry15 as an example):
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), magnesium tert-butoxide (0.9mg, 0.005mmol, 5 mol%), alpha, beta-unsaturated ketone 1a (20.8mg, 0.1mmol) and organic boric acid 2a (17.8mg, 0.12mmol, 1.2equiv), purged 3 times, then dried methyl tert-butyl ether (1.0mL) was added and stirred at 25 ℃ for 24 h. TLC point plate tracking until the raw material 1a disappears, adding 0.1mL water to quench the reaction, removing solvent under reduced pressure, and directly separating and purifying by fast silica gel column chromatography (eluent is dichloromethane/petroleum ether volume ratio 1/5) to obtain the target product 3aa, with 99% yield and 96% ee.
3aa white solid (31.0mg, 99% yield); mp68-71 ℃; HPLC (DaicelChiralcel OD-H, n-hexyl)Alkane/isopropanol 95:5, flow rate 0.8mL/min, λ 254nm) tR(minor)＝12.62min,tR(major)＝15.62min,ee＝96％；[α]D 17＝1.3(c2.0,CH2Cl2)；1HNMR(400MHz,CDCl3)δ7.94(d,J＝7.6Hz,2H),7.56-7.42(m,3H)，7.33-7.15(m,10H),6.45-6.36(m,2H),4.30(q,J＝5.2Hz,1H),3.55-3.44(m,2H)；HRMS(ESI)calcd.forC23H20ONa([M+Na]+):335.1406,found:335.1402.
Example 2:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), magnesium tert-butoxide (0.9mg, 0.005mmol, 5 mol%), alpha, beta-unsaturated ketone 1b (22.2mg, 0.1mmol) and organic boric acid 2a (17.8mg, 0.12mmol, 1.2equiv), purged 3 times, then dried methyl tert-butyl ether (1.0mL) was added and stirred at 25 ℃ for 48 h. TLC point plate tracking until the raw material 1b disappears, adding 0.1mL water to quench the reaction, removing solvent under reduced pressure, and separating and purifying by direct flash silica gel column chromatography (eluent is dichloromethane/petroleum ether volume ratio 1/5) to obtain the target product 3ba, yield 92%, 96% ee.
3ba colorless oily liquid (30.0mg, 92% yield); HPLC (DaicelChiralcel OD-H, n-hexane/isopropanol 90:10, flow rate 0.8mL/min,. lambda.254 nm) tR(minor)＝8.05min,tR(major)＝9.74min,ee＝96％；[α]D 22＝0.6(c1.0,CHCl3)；1HNMR(400MHz,CDCl3)δ7.94(q,J＝8.4Hz,2H),7.57-7.43(m,4H),7.31-7.12(m,8H),6.43-6.34(m,2H),4.26(q,J＝5.2Hz,1H),3.54-3.42(m,2H),2.32(s,3H).HRMS(ESI)calcd.forC24H22ONa([M+Na]+):349.1563,found:349.1572.
Example 3:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), magnesium tert-butoxide (0.9mg, 0.005mmol, 5 mol%), alpha, beta-unsaturated ketone 1c (22.2mg, 0.1mmol) and organic boric acid 2a (17.8mg, 0.12mmol, 1.2equiv), purged 3 times, then dried methyl tert-butyl ether (1.0mL) was added and stirred at 25 ℃ for 24 h. TLC point plate tracking until the raw material 1c disappears, adding 0.1mL water to quench the reaction, removing solvent under reduced pressure, and directly separating and purifying by fast silica gel column chromatography (eluent is dichloromethane/petroleum ether volume ratio 1/5) to obtain the target product 3ca with 99% yield and 96% ee.
3ca as a colorless oily liquid (34.0mg, 99% yield); HPLC (DaicelChiralcel OD-H, n-hexane/isopropanol 90:10, flow rate 0.8mL/min,. lambda.254 nm) tR(minor)＝10.57min,tR(major)＝13.77min,ee＝96％；[α]D 21＝9.6(c2.0,CH2Cl2)；1HNMR(400MHz,CDCl3)δ7.96-7.93(m,2H),7.57-7.43(m,3H),7.31-7.15(m,7H),6.87-6.84(m,2H),6.43-6.33(m,2H),4.25(q,J＝5.6Hz,1H),3.78(s,3H),3.52-3.43(m,2H)；HRMS(ESI)calcd.forC24H22O2Na([M+Na]+):365.1512,found:365.1511.
Example 4:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), tertiaryMagnesium butoxide (0.9mg, 0.005mmol, 5 mol%), α, β -unsaturated ketone 1d (28.7mg, 0.1mmol) and organoboronic acid 2a (17.8mg, 0.12mmol, 1.2equiv), purged 3 times, then dry methyl t-butyl ether (1.0mL) was added and stirred at 25 ℃ for 40 h. TLC point plate tracking until the raw material 1d disappears, adding 0.1mL water to quench the reaction, removing solvent under reduced pressure, and direct fast silica gel column chromatography (eluent is dichloromethane/petroleum ether volume ratio 1/5) to separate and purify to obtain the target product 3da, yield 97%, 96% ee.
3da as a colorless oily liquid (38.1mg, 97% yield); HPLC (DaicelChiralcel OD-H, n-hexane/isopropanol 90:10, flow rate 0.8mL/min,. lambda.254 nm) tR(minor)＝9.91min,tR(major)＝14.29min,ee＝96％；[α]D 21＝0.5(c2.0,CH2Cl2)；1HNMR(600MHz,CDCl3)δ7.94-7.92(m,2H),7.56-7.53(m,1H),7.46-7.41(m,4H),7.31-7.24(m,4H),7.20-7.17(m,3H),4.27(q,J＝4.8Hz,1H),3.51-3.43(m,2H)；13C{1H}NMR(150MHz,CDCl3)δ197.8,142.4,137.09,137.07,133.3,132.1,131.8,130.5,129.7,128.8,128.6,128.2,127.6,126.4,120.5,44.3,43.4；HRMS(ESI)calcd.forC23H19OBrNa([M+Na]+):413.0511,found:413.0493.
Example 5:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), magnesium tert-butoxide (0.9mg, 0.005mmol, 5 mol%), alpha, beta-unsaturated ketone 1e (25.3mg, 0.1mmol) and organic boric acid 2a (17.8mg, 0.12mmol, 1.2equiv), then purging 3 times, adding dry methyl tert-butyl ether (1.0mL), stirring at 25 ℃ for 40 h. TLC plate tracking till raw material 1e disappears, quenching with 0.1mL water, removing solvent under reduced pressure, and performing rapid silica gel column chromatography (eluent is dichlorine)Methane/petroleum ether volume ratio 1/2) to obtain the target product 3ea with a yield of 99% and 96% ee.
3ea yellow solid (35.6mg, 99% yield); mp80-83 deg.C; HPLC (DaicelChiralcel OD-H, n-hexane/isopropanol 85:15, flow rate 0.8mL/min,. lambda.254 nm) tR(minor)＝21.38min,tR(major)＝34.64min,ee＝96％；[α]D 16＝-2.1(c2.0,CH2Cl2)；1HNMR(400MHz,CDCl3)δ8.20-8.17(m,2H),7.95-7.93(m,2H),7.60-7.45(m,5H),7.33-7.22(m,5H),6.46-6.34(m,2H),4.43(q,J＝6.8Hz,1H),3.61-3.51(m,2H)；HRMS(ESI)calcd.forC23H19NO3Na([M+Na]+):380.1257,found:380.1253.
Example 6:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), magnesium tert-butoxide (0.9mg, 0.005mmol, 5 mol%), alpha, beta-unsaturated ketone 1f (25.8mg, 0.1mmol) and organic boric acid 2a (17.8mg, 0.12mmol, 1.2equiv), then purging 3 times, adding dry methyl tert-butyl ether (1.0mL), stirring at 25 ℃ for 48 h. TLC point plate tracking until raw material 1f disappears, adding 0.1mL water to quench reaction, removing solvent under reduced pressure, and separating and purifying by direct flash silica gel column chromatography (eluent is dichloromethane/petroleum ether volume ratio 1/5) to obtain target product 3fa with yield of 92% and 96% ee.
3fa as a white solid (33.4mg, 92% yield); mp106-108 ℃; HPLC (DaicelChiralcel OD-H, n-hexane/isopropanol 90:10, flow rate 0.8mL/min,. lambda.254 nm) tR(minor)＝12.44min,tR(major)＝14.19min,ee＝96％；[α]D 21＝0.6(c1.0,CH2Cl2)；1HNMR(600MHz,CDCl3)δ7.96-7.94(m,2H),7.81-7.78(m,3H),7.75(s,1H),7.55-7.52(m,1H),7.47-7.41(m,5H),7.31-7.23(m,4H),7.19-7.16(m,1H),6.51-6.41(m,2H),4.48(q,J＝6.6Hz,1H),3.63-3.55(m,2H)；13CNMR(150MHz,CDCl3)δ198.2,140.8,137.30,137.27,133.7,133.2,132.6,132.5,130.5,128.8,128.6,128.5,128.2,127.8,127.7,127.4,126.5,126.4,126.2,125.7,44.5,44.1；HRMS(ESI)calcd.forC27H22ONa([M+Na]+):385.1563,found:385.1558.
Example 7:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), magnesium tert-butoxide (0.9mg, 0.005mmol, 5 mol%), alpha, beta-unsaturated ketone 1g (21.4mg, 0.1mmol) and organic boric acid 2a (17.8mg, 0.12mmol, 1.2equiv), purged 3 times, then dried methyl tert-butyl ether (1.0mL) was added and stirred at 25 ℃ for 36 h. TLC point plate tracking until 1g of raw material disappears, adding 0.1mL of water to quench the reaction, removing solvent under reduced pressure, and separating and purifying by direct fast silica gel column chromatography (eluent is dichloromethane/petroleum ether volume ratio 1/5) to obtain the target product 3 ga.
3ga white solid (30.3mg, 95% yield); mp78-80 ℃; HPLC (DaicelChiralcel OD-H, n-hexane/isopropanol 90:10, flow rate 0.8mL/min,. lambda.254 nm) tR(minor)＝9.76min,tR(major)＝12.03min,ee＝95％；[α]D 19＝-5.4(c1.0,CHCl3)；1HNMR(400MHz,CDCl3)δ7.97-7.94(m,2H),7.57-7.43(m,3H),7.34-7.15(m,6H),6.95-6.91(m,2H),6.50-6.35(m,2H),4.63-4.58(m,1H),3.59-3.46(m,2H)；13C{1H}NMR(150MHz,CDCl3)δ197.7,147.2,137.15,137.07,133.3,131.9,130.8,128.8,128.6,128.2,127.6,127.0,126.5,124.2,123.9,45.6,39.4；HRMS(ESI)calcd.forC21H18OSNa([M+Na]+):341.0971,found:341.0968.
Example 8:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), magnesium tert-butoxide (0.9mg, 0.005mmol, 5 mol%), alpha, beta-unsaturated ketone 1h (19.8mg, 0.1mmol) and organic boric acid 2a (17.8mg, 0.12mmol, 1.2equiv), degassing 3 times, adding dried methyl tert-butyl ether (1.0mL), stirring at 25 deg.C for 36 h. TLC point plate tracking until the raw material disappears for 1h, adding 0.1mL water to quench the reaction, removing the solvent under reduced pressure, and directly separating and purifying by flash column chromatography (the eluent is dichloromethane/petroleum ether with volume ratio of 1/5) to obtain the target product 3 ha.
3ha white solid (28.0mg, 93% yield); mp87-89 ℃; HPLC (DaicelChiralcel OD-H, n-hexane/isopropanol 90:10, flow rate 0.8mL/min,. lambda.254 nm) tR(minor)＝8.54min,tR(major)＝9.87min,ee＝97％；[α]D 21＝-22.0(c1.0,CHCl3)；1HNMR(400MHz,CDCl3)δ7.96(d,J＝8.4Hz,2H),7.57-7.43(m,3H),7.33-7.17(m,6H),6.49-6.29(m,3H),6.11(d,J＝3.2Hz,1H),4.39(q,J＝6.8Hz,1H),3.57(dd,J＝16.8,6.4Hz,1H),3.40(dd,J＝16.8,7.6Hz,1H)；13C{1H}NMR(150MHz,CDCl3)δ197.8,156.1,141.6,137.1,133.3,131.5,129.6,128.8,128.6,128.2,127.5,126.5,110.4,105.6,42.5,38.0；HRMS(ESI)calcd.forC21H18O2Na([M+Na]+):325.1199,found:325.1192.
Example 9:
in the presence of nitrogen gasWhile protecting, 100mg of a 25mL Schlenk tube subjected to anhydrous and anaerobic treatment was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), magnesium tert-butoxide (0.9mg, 0.005mmol, 5 mol%), alpha, beta-unsaturated ketone 1i (23.8mg, 0.1mmol) and organic boric acid 2a (17.8mg, 0.12mmol, 1.2equiv), purged 3 times, then dried methyl tert-butyl ether (1.0mL) was added and stirred at 25 ℃ for 36 h. TLC point plate tracking until the raw material 1i disappears, adding 0.1mL water to quench the reaction, removing solvent under reduced pressure, and separating and purifying by direct fast silica gel column chromatography (eluent is dichloromethane/petroleum ether volume ratio 1/5) to obtain the target product 3 ia.
3ia white solid (34.0mg, 99% yield); mp122-125 ℃; HPLC (DaicelChiralcel OD-H, n-hexane/isopropanol 85:15, flow rate 0.8mL/min,. lambda.254 nm) tR(minor)＝12.54min,tR(major)＝22.93min,ee＝94％；[α]D 17＝5.6(c2.0,CH2Cl2)；1HNMR(400MHz,CDCl3)δ7.95-7.91(m,2H),7.33-7.15(m,10H),6.94-6.89(m,2H),6.45-6.35(m,2H),4.30(q,J＝5.6Hz,1H),3.86(s,3H),3.46-3.43(m,2H)；HRMS(ESI)calcd.forC24H22O2Na([M+Na]+):365.1512,found:365.1510.
Example 10:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), magnesium tert-butoxide (0.9mg, 0.005mmol, 5 mol%), alpha, beta-unsaturated ketone 1j (14.6mg, 0.1mmol) and organic boric acid 2a (17.8mg, 0.12mmol, 1.2equiv), purged 3 times, then dried methyl tert-butyl ether (1.0mL) was added and stirred at 25 ℃ for 48 h. TLC plate tracking until 1j of starting material disappears, add 0And carrying out water quenching reaction by 1mL, removing the solvent under reduced pressure, and then directly carrying out fast silica gel column chromatography (an eluent is 1/5 in a volume ratio of dichloromethane to petroleum ether) for separation and purification to obtain the target product 3 ja.
3ja as a colorless oily liquid (24.8mg, 99% yield); HPLC (DaicelChiralcel OD-H, n-hexane/isopropanol 90:10, flow rate 0.8mL/min,. lambda.254 nm) tR(minor)＝9.19min,tR(major)＝10.37min,ee＝96％；[α]D 21＝13.3(c2.0,CH2Cl2)；1HNMR(400MHz,CDCl3)δ7.34-7.17(m,10H),6.40-6.29(m,2H),4.08(q,J＝6.8Hz,1H),3.00-2.89(m,2H),2.11(s,3H)；HRMS(ESI)calcd.forC18H18ONa([M+Na]+):273.1250,found:273.1250.
Example 11:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), magnesium tert-butoxide (0.9mg, 0.005mmol, 5 mol%), alpha, beta-unsaturated ketone 1k (20.4mg, 0.1mmol) and organic boric acid 2a (17.8mg, 0.12mmol, 1.2equiv), purged 3 times, then dried methyl tert-butyl ether (1.0mL) was added and stirred at 25 ℃ for 48 h. TLC point plate tracking until 1k of raw material disappears, adding 0.1mL water to quench reaction, removing solvent under reduced pressure, and separating and purifying by direct fast silica gel column chromatography (eluent is dichloromethane/petroleum ether volume ratio 1/5) to obtain target product 3 ka.
3ka white solid (30.7mg, 99% yield); mp75-77 deg.C; HPLC (DaicelChiralcel OD-H, n-hexane/isopropanol 85:15, flow rate 0.8mL/min,. lambda.254 nm) tR(minor)＝9.91min,tR(major)＝10.52min,ee＝94％；[α]D 17＝-42.5(c2.0,CH2Cl2)；1HNMR(400MHz,CDCl3)δ8.00-7.97(m,2H),7.59-7.55(m,1H),7.49-7.45(m,2H),7.38-7.29(m,4H),7.25-7.21(m,1H),6.60(d,J＝16.0Hz,1H),6.28(dd,J＝15.6,8.0Hz,1H),4.23-4.16(m,2H),3.90-3.85(m,1H),3.69(dd,J＝17.6,8.8Hz,1H),3.25(dd,J＝17.6,4.8Hz,1H),1.28(t,J＝7.2Hz,3H)；HRMS(ESI)calcd.forC20H20O3Na([M+Na]+):331.1305,found:331.1300.
Example 12:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.01mmol, 10 mol%), magnesium tert-butoxide (1.7mg, 0.01mmol, 10 mol%), alpha, beta-unsaturated ketone 1a (20.8mg, 0.1mmol) and organic boric acid 2b (13.4mg, 0.12mmol, 1.2equiv), purged 3 times, then dried methyl tert-butyl ether (1.0mL) was added and stirred at 25 ℃ for 36 h. TLC point plate tracking until the raw material 1a disappears, adding 0.1mL water to quench reaction, removing solvent under reduced pressure, and separating and purifying by direct fast silica gel column chromatography (eluent is dichloromethane/petroleum ether volume ratio 1/5) to obtain the target product 3 ab.
3ab white solid (27.6mg, 99% yield); mp70-73 ℃; HPLC (DaicelChiralpakAD-H, n-hexane/isopropanol 95:5, flow rate 0.8mL/min,. lambda.254 nm) tR(minor)＝11.23min,tR(major)＝11.99min,ee＝86％；[α]D 14＝30.8(c2.0,CH2Cl2)；1HNMR(400MHz,CDCl3)δ7.95-7.92(m,2H),7.57-7.53(m,1H),7.46-7.42(m,2H),7.32-7.28(m,5H),7.22-7.19(m,1H),6.26(dd,J＝3.2,2.0Hz,1H),6.03(d,J＝3.2Hz,1H),4.84(t,J＝7.2Hz,1H),3.82(dd,J＝17.2,7.2Hz,1H),3.56(dd,J＝17.2,7.2Hz,1H)；HRMS(ESI)calcd.forC19H16O2Na([M+Na]+):299.1043,found:299.1043.
Example 13:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.01mmol, 10 mol%), magnesium tert-butoxide (1.7mg, 0.01mmol, 10 mol%), alpha, beta-unsaturated ketone 1a (20.8mg, 0.1mmol) and organic boric acid 2c (19.4mg, 0.12mmol, 1.2equiv), purged 3 times, then dried methyl tert-butyl ether (1.0mL) was added and stirred at 25 ℃ for 48 h. TLC point plate tracking until the raw material 1a disappears, adding 0.1mL water to quench the reaction, removing the solvent under reduced pressure, and directly separating and purifying by fast silica gel column chromatography (the eluent is dichloromethane/petroleum ether with volume ratio of 1/5) to obtain the target product 3 ac.
3ac white solid (32.2mg, 99% yield); mp86-88 ℃; HPLC (DaicelChiralpakID, 95:5 n-hexane/isopropanol, flow rate 0.8mL/min, 254nm) tR(major)＝14.05min,tR(minor)＝15.19min,ee＝87％；[α]D 15＝42.7(c2.0,CH2Cl2)；1HNMR(400MHz,CDCl3)δ7.97-7.94(m,2H),7.55-7.53(m,1H),7.46-7.29(m,8H),7.25-7.13(m,3H),6.43(s,1H),4.98(t,J＝7.2Hz,1H),3.93(dd,J＝17.6,7.2Hz,1H),3.66(dd,J＝17.6,7.2Hz,1H)；HRMS(ESI)calcd.forC23H18O2Na([M+Na]+):349.1199,found:349.1194.
Example 14:
under the protection of nitrogen, 100mg of anhydrous oxygen-free treated 25mLSchlen tube was added
Molecular sieve, chiral catalyst Cat1(2.5mg, 0.005mmol, 5 mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5 mol%), alpha, beta-unsaturatedKetone 1a (20.8mg, 0.1mmol) and organoboronic acid 2d (18.7mg, 0.12mmol, 1.2equiv), were degassed 3 times, and then dried methyl t-butyl ether (1.0mL) was added and stirred at 25 ℃ for 72 h. TLC point plate tracking until the raw material 1a disappears, adding 0.1mL water to quench the reaction, removing the solvent under reduced pressure, and directly separating and purifying by fast silica gel column chromatography (the eluent is dichloromethane/petroleum ether with volume ratio of 1/5) to obtain the target product 3 ad.
3ad as a colorless oily liquid (18.2mg, 57% yield); HPLC (DaicelChiralcel OD-H, n-hexane/isopropanol 95:5, flow rate 0.5mL/min,. lambda.254 nm) tR(minor)＝8.79min,tR(major)＝9.39min,ee＝96％；[α]D 18＝-8.2(c0.3,CHCl3)；1HNMR(400MHz,CDCl3)δ7.93-7.90(m,2H),7.56-7.52(m,1H),7.46-7.42(m,2H),7.31-7.24(m,4H),7.21-7.17(m,1H),5.64-5.58(m,1H),5.46-5.41(m,1H),4.06(q,J＝7.2Hz,1H),3.42-3.29(m,2H),1.95(q,J＝6.8Hz,2H),1.30-1.18(m,8H),0.85(t,J＝7.2Hz,3H)；HRMS(ESI)calcd.forC23H28ONa([M+Na]+):343.2032,found:343.2035.
The foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (6)
1. The method for synthesizing the optically active ketone compound by the asymmetric conjugate addition reaction of the organic boric acid and the alpha, beta-unsaturated ketone is characterized in that the reaction equation is as follows:
the method comprises the following specific steps: alpha, beta-unsaturated ketone 1 and organic boric acid 2 are taken as raw materials, and chiral tetraphenyl cyclooctatetraene compounds, molecular sieve and magnesium tert-butoxide additives exist in the presence of catalyst chiral tetraphenyl cyclooctatetraene compoundsObtaining ketone compounds through asymmetric conjugate addition reaction, wherein R1= phenyl, substituted phenyl, methyl; r2= phenyl, substituted phenyl, 2-thienyl, 2-furyl, 1-naphthyl, 2-naphthyl, ester group, R3The catalyst chiral tetraphenylcyclooctyltetraene compound is one of Cat1, Cat 2, Cat 3 and Cat 4, and the specific structures of Cat1, Cat 2, Cat 3 and Cat 4 are as follows:
2. the method for synthesizing optically active ketone compounds according to claim 1, wherein R is selected from the group consisting of1Selected from Ph, 4-CH3OC6H4、4-BrC6H4Or Me; r2Selected from Ph, 4-CH3OC6H4、4-FC6H4、4-ClC6H4、4-BrC6H4、2-BrC6H4、4-CF3C6H4、4-NO2C6H42-thienyl, 2-furyl, 1-naphthyl, 2-naphthyl or CO2Et； R3Is selected from
、
、
Or
。
3. The method for synthesizing optically active ketone compounds by asymmetric conjugate addition reaction of organic boric acid and α, β -unsaturated ketone according to claim 1, wherein the molar ratio of α, β -unsaturated ketone 1, organic boric acid 2, catalyst and magnesium tert-butoxide is 1:1.2:0.05: 0.05.
4. The method for synthesizing optically active ketone compounds by asymmetric conjugate addition reaction of organic boronic acid and α, β -unsaturated ketone according to claim 1, wherein the reaction solvent is one selected from the group consisting of methyl t-butyl ether, toluene, dichloromethane, tetrahydrofuran, trifluorotoluene, o-xylene, 1, 2-dichloroethane, diisopropyl ether, 1, 4-dioxane and acetonitrile.
5. The method for synthesizing optically active ketone compounds by the asymmetric conjugate addition reaction of organic boric acid and α, β -unsaturated ketone according to claim 1, wherein the reaction temperature is 0 to 25 ℃.
6. The method for synthesizing optically active ketone compounds by the asymmetric conjugate addition reaction of organic boric acid and α, β -unsaturated ketone according to claim 1, wherein the whole reaction process is carried out in a nitrogen or argon atmosphere.
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