CN110054553A - The method that organic boronic reacts synthesizing optical activity ketone compounds with the asymmetric conjugated reaction of alpha, beta-unsaturated ketone - Google Patents

The method that organic boronic reacts synthesizing optical activity ketone compounds with the asymmetric conjugated reaction of alpha, beta-unsaturated ketone Download PDF

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CN110054553A
CN110054553A CN201910457453.XA CN201910457453A CN110054553A CN 110054553 A CN110054553 A CN 110054553A CN 201910457453 A CN201910457453 A CN 201910457453A CN 110054553 A CN110054553 A CN 110054553A
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柴国利
汪娟
张苹
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Henan Normal University
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Abstract

Organic boronic and α, the method for the asymmetric conjugated reaction reaction synthesizing optical activity ketone compounds of alpha, beta-unsaturated ketone, belong to the asymmetric syntheses technical field in organic chemistry, reaction equation is as follows:Specific step is as follows: with α, alpha, beta-unsaturated ketone 1 and organic boronic 2 are raw material, in the chiral four benzo cyclo-octatetraene class compounds of catalyst, and in the presence of molecular sieve and tert-butyl alcohol magnesium additive, it reacts to obtain ketone compounds by asymmetric conjugated reaction, wherein R1=phenyl, substituted-phenyl, methyl；R2=phenyl, substituted-phenyl, 2- thienyl, 2- furyl, 1- naphthalene, 2- naphthalene, ester group, R3=styryl, 2- furyl, 2- benzofuranyl, positive octenyl.Present invention has an advantage that reaction raw materials are easy to get, catalyst structure is novel, and high catalytic efficiency, reaction condition is mild, and post-processing is simple, obtains high optical activity ketone compounds.

Description

It is living that organic boronic reacts synthesizing optical with the asymmetric conjugated reaction of alpha, beta-unsaturated ketone The method of property ketone compounds
Technical field
The invention belongs to the asymmetric syntheses technical fields in organic chemistry, and in particular to a kind of chiral four benzo ring pungent four Vinyl compound is catalyzed organic boronic and α, and the asymmetric conjugated reaction reaction of alpha, beta-unsaturated ketone is closed with enantioselectivity in high yield At the method for optical activity ketone compounds.
Background technique
It is construct C-C key important that organic boride is reacted with the asymmetric conjugated reaction of alpha, beta-unsaturated carbonyl compound One of synthetic method (Molecules2018,23,2317.).Organic boride (borinic acid, organic boric acid ester and organic boronic Salt) the advantages that, stability less toxic, cheap and easy to get with it is good and good functional group tolerance plays weight in modern organic synthesis It acts on, organocatalysis organic boride and α, the asymmetric conjugated reaction of beta-unsaturated carbonyl compound reacts ((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.2015,54,9931； (f) Chem.Commun.2010,46,7799.) there is lot of advantages, for example, catalyst hypotoxicity, it is easily prepared, cheap, Stability is good, easy to operate and there is no metal residuals after reaction etc..
Up to the present, also fewer for the chiral catalyst type of the reaction, and need use less steady mostly Fixed organic boric acid ester and organic borate, it is directly also fewer using the report of simple and easy to get, metastable organic boronic. Therefore, the catalyst system that development is efficiently participated in without transition metal realizes organic boronic and α, the asymmetric conjugation of alpha, beta-unsaturated ketone Addition reaction obtains a series of optically active ketone compounds, has important research significance.
Summary of the invention
The purpose of the present invention is to provide a kind of organic boronics to react conjunction with the asymmetric conjugated reaction of alpha, beta-unsaturated ketone At the method for optical activity ketone compounds.
Based on above-mentioned purpose, the present invention uses organic boronic and α, and alpha, beta-unsaturated ketone is as raw material, in chiral four benzo rings Octatetraene class compound reacts, with height under molecular sieve and tert-butyl alcohol magnesium additive by asymmetric conjugated reaction as catalyst Yield and enantioselectivity one-step synthesis optical activity ketone compounds.
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-NO2C6H4, 2- thienyl, 2- furyl, 1- naphthalene, 2- naphthalene or CO2Et；R3Choosing From
Further, in the above-mentioned technical solutions, the chiral catalyst is selected from (S, S) -1,8,9,16- tetrahydroxy, four benzene And cyclo-octatetraene ((S, S)-THTP), four benzo cyclo-octatetraene of (S) -1,16- dihydroxy ((S)-DHTP), (S) -2,15- bis- is bromo- Four benzo cyclo-octatetraene of 1,16- dihydroxy ((S) -2,15-Br2- DHTP), and (S) -2,15- diphenyl -1,16- dihydroxy four Benzo cyclo-octatetraene ((S) -2,15-Ph2One of-DHTP).The synthesis of chiral four benzo cyclo-octatetraene catalyst is according to ginseng Examine document (J.Org.Chem.2019,84,120.) synthesis.It is as follows that catalyst respectively corresponds specific structure:
Further, in the above-mentioned technical solutions, the α, alpha, beta-unsaturated ketone 1, organic boronic 2, catalyst, tert-butyl alcohol magnesium Molar ratio be 1:1.2:0.05:0.05, every 0.1mmol α, the dosage of molecular sieve is 100mg in alpha, beta-unsaturated ketone 1.
Further, in the above-mentioned technical solutions, the reaction dissolvent is toluene, methylene chloride, tetrahydrofuran, methyl- tert Butyl ether (MTBE), benzotrifluoride, ortho-xylene (o-xylene), 1,2- dichloroethanes (DCE), Di Iso Propyl Ether, 1,4- bis- One of six ring of oxygen and acetonitrile.
Further, in the above-mentioned technical solutions, reaction temperature is 0 to 25 DEG C, preferably 25 DEG C.
Further, in the above-mentioned technical solutions, entire reaction process needs carry out under nitrogen or argon atmosphere, preferably Nitrogen.
Invention the utility model has the advantages that
Reaction raw materials of the present invention are easy to get, and reaction condition is mild, and post-processing is simple, and catalyst is recyclable to be recycled, and product is received Rate and enantioselectivity are well to outstanding.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment, but protection model of the invention It encloses and is not limited thereto.
Embodiment 1:
aUnless otherwise indicated, trans--chalcone 1a (0.1mmol), trans- -2- phenylvinylboronic acid 2a (0.12mmol), catalyst (0.01mmol), Mg (OtBu)2(0.01mmol),Molecular sieve (100mg), and 1.0mL are anhydrous Solvent is in N2Is stirred under atmospherebSeparate yieldcEe value obtains by chiral column HPLC chiral analysisdIn 0 DEG C ofeCat1 (0.005mmol, 5mol%), Mg (OtBu)2(0.005mmol, 5mol%)fCat1 (0.002mmol, 2mol%), Mg (OtBu)2(0.002mmol, 2mol%)
In the screening process of reaction condition, influence (entries1-10) of the different solvents to reaction has been primarily looked at, Final choice methyl tertiary butyl ether(MTBE) makees solvent.Then, influence (entries11- of the different chiral catalysts to reaction has been investigated 13), finally it has been determined that Cat1 is optimum catalyst.The influence of temperature, catalyst amount to reaction has been investigated simultaneously (entries14-16), final choice reaction temperature is 25 DEG C, catalyst amount 5mol%.
The investigation (by taking entry15 as an example) of reaction condition:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1a (20.8mg, 0.1mmol) and organic boronic 2a (17.8mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirrings are for 24 hours.TLC contact plate tracks to raw material 1a disappearance, and 0.1mL water quenching is added to go out It is pure that directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent in reaction Change obtains target product 3aa, yield 99%, 96%ee.
3aa white solid (31.0mg, yield 99%)；mp68-71℃；HPLC (DaicelChiralcelOD-H, just oneself Alkane/isopropanol=95:5, flow velocity 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) δ 7.94 (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.
Embodiment 2:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1b (22.2mg, 0.1mmol) and organic boronic 2a (17.8mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 48h.TLC contact plate tracks to raw material 1b disappearance, and 0.1mL water quenching is added to go out It is pure that directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent in reaction Change obtains target product 3ba, yield 92%, 96%ee.
3ba colourless oil liquid (30.0mg, yield 92%)；HPLC (DaicelChiralcelOD-H, n-hexane/isopropyl Alcohol=90:10, flow velocity 0.8mL/min, λ=254nm) tR(minor)=8.05min, tR(major)=9.74min, ee= 96%；[α]D 22=0.6 (c1.0, CHCl3)；1HNMR(400MHz,CDCl3) δ 7.94 (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.
Embodiment 3:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1c (22.2mg, 0.1mmol) and organic boronic 2a (17.8mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirrings are for 24 hours.TLC contact plate tracks to raw material 1c disappearance, and 0.1mL water quenching is added to go out It is pure that directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent in reaction Change obtains target product 3ca, yield 99%, 96%ee.
3ca colourless oil liquid (34.0mg, yield 99%)；HPLC (DaicelChiralcelOD-H, n-hexane/isopropyl Alcohol=90:10, flow velocity 0.8mL/min, λ=254nm) 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.
Embodiment 4:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1d (28.7mg, 0.1mmol) and organic boronic 2a (17.8mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 40h.TLC contact plate tracks to raw material 1d disappearance, and 0.1mL water quenching is added to go out It is pure that directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent in reaction Change obtains target product 3da, yield 97%, 96%ee.
3da colourless oil liquid (38.1mg, yield 97%)；HPLC (DaicelChiralcelOD-H, n-hexane/isopropyl Alcohol=90:10, flow velocity 0.8mL/min, λ=254nm) 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.
Embodiment 5:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1e (25.3mg, 0.1mmol) and organic boronic 2a (17.8mg, 0.12mmol, 1.2equiv), then substitute gas 3 times, then Dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 40h are added.TLC contact plate tracks to raw material 1e disappearance, adds 0.1mL water quenching It goes out reaction, directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/2) separation is removed under reduced pressure after solvent Purifying obtains target product 3ea, yield 99%, 96%ee.
3ea yellow solid (35.6mg, yield 99%)；mp80-83℃；HPLC (DaicelChiralcelOD-H, just oneself Alkane/isopropanol=85:15, flow velocity 0.8mL/min, λ=254nm) 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.
Embodiment 6:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1f (25.8mg, 0.1mmol) and organic boronic 2a (17.8mg, 0.12mmol, 1.2equiv), then substitute gas 3 times, then Dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 48h are added.TLC contact plate tracks to raw material 1f disappearance, adds 0.1mL water quenching It goes out reaction, directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent Purifying obtains target product 3fa, yield 92%, 96%ee.
3fa white solid (33.4mg, yield 92%)；mp106-108℃；HPLC (DaicelChiralcelOD-H, just Hexane/isopropyl alcohol=90:10, flow velocity 0.8mL/min, λ=254nm) 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.
Embodiment 7:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1g (21.4mg, 0.1mmol) and organic boronic 2a (17.8mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 36h.TLC contact plate tracks to raw material 1g disappearance, and 0.1mL water quenching is added to go out It is pure that directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent in reaction Change obtains target product 3ga.
3ga white solid (30.3mg, yield 95%)；mp78-80℃；HPLC (DaicelChiralcelOD-H, just oneself Alkane/isopropanol=90:10, flow velocity 0.8mL/min, λ=254nm) 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.
Embodiment 8:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1h (19.8mg, 0.1mmol) and organic boronic 2a (17.8mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 36h.TLC contact plate tracks to raw material 1h disappearance, and 0.1mL water quenching is added to go out Reaction is removed under reduced pressure after solvent directly rapid column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) and isolates and purifies To target product 3ha.
3ha white solid (28.0mg, yield 93%)；mp87-89℃；HPLC (DaicelChiralcelOD-H, just oneself Alkane/isopropanol=90:10, flow velocity 0.8mL/min, λ=254nm) tR(minor)=8.54min, tR(major)=9.87min, Ee=97%；[α]D 21=-22.0 (c1.0, CHCl3)；1HNMR(400MHz,CDCl3) δ 7.96 (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.
Embodiment 9:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1i (23.8mg, 0.1mmol) and organic boronic 2a (17.8mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 36h.TLC contact plate tracks to raw material 1i disappearance, and 0.1mL water quenching is added to go out It is pure that directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent in reaction Change obtains target product 3ia.
3ia white solid (34.0mg, yield 99%)；mp122-125℃；HPLC (DaicelChiralcelOD-H, just Hexane/isopropyl alcohol=85:15, flow velocity 0.8mL/min, λ=254nm) 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.
Embodiment 10:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1j (14.6mg, 0.1mmol) and organic boronic 2a (17.8mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 48h.TLC contact plate tracks to raw material 1j disappearance, and 0.1mL water quenching is added to go out It is pure that directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent in reaction Change obtains target product 3ja.
3ja colourless oil liquid (24.8mg, yield 99%)；HPLC (DaicelChiralcelOD-H, n-hexane/isopropyl Alcohol=90:10, flow velocity 0.8mL/min, λ=254nm) 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.
Embodiment 11:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1k (20.4mg, 0.1mmol) and organic boronic 2a (17.8mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 48h.TLC contact plate tracks to raw material 1k disappearance, and 0.1mL water quenching is added to go out It is pure that directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent in reaction Change obtains target product 3ka.
3ka white solid (30.7mg, yield 99%)；mp75-77℃；HPLC (DaicelChiralcelOD-H, just oneself Alkane/isopropanol=85:15, flow velocity 0.8mL/min, λ=254nm) 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.
Embodiment 12:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.01mmol, 10mol%), tert-butyl alcohol magnesium (1.7mg, 0.01mmol, 10mol%), α, β-is no Saturated ketone 1a (20.8mg, 0.1mmol) and organic boronic 2b (13.4mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 36h.TLC contact plate tracks to raw material 1a disappearance, and 0.1mL water quenching is added to go out It is pure that directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent in reaction Change obtains target product 3ab.
3ab white solid (27.6mg, yield 99%)；mp70-73℃；HPLC (DaicelChiralpakAD-H, just oneself Alkane/isopropanol=95:5, flow velocity 0.8mL/min, λ=254nm) 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.
Embodiment 13:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.01mmol, 10mol%), tert-butyl alcohol magnesium (1.7mg, 0.01mmol, 10mol%), α, β-is no Saturated ketone 1a (20.8mg, 0.1mmol) and organic boronic 2c (19.4mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 48h.TLC contact plate tracks to raw material 1a disappearance, and 0.1mL water quenching is added to go out It is pure that directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent in reaction Change obtains target product 3ac.
3ac white solid (32.2mg, yield 99%)；mp86-88℃；HPLC (DaicelChiralpakID, n-hexane/ Isopropanol=95:5, flow velocity 0.8mL/min, λ=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.
Embodiment 14:
Under nitrogen protection, 100mg is added into the 25mLSchlenk pipe handled by anhydrous and oxygen-freeMolecular sieve, hand Property catalyst Cat1 (2.5mg, 0.005mmol, 5mol%), tert-butyl alcohol magnesium (0.9mg, 0.005mmol, 5mol%), α, β-is no Saturated ketone 1a (20.8mg, 0.1mmol) and organic boronic 2d (18.7mg, 0.12mmol, 1.2equiv) substitutes gas 3 times, then plus Enter dry methyl tertiary butyl ether(MTBE) (1.0mL), 25 DEG C of stirring 72h.TLC contact plate tracks to raw material 1a disappearance, and 0.1mL water quenching is added to go out It is pure that directly Flash silica column chromatography (eluant, eluent is methylene chloride/petroleum ether volume ratio 1/5) separation is removed under reduced pressure after solvent in reaction Change obtains target product 3ad.
3ad colourless oil liquid (18.2mg, yield 57%)；HPLC (DaicelChiralcelOD-H, n-hexane/isopropyl Alcohol=95:5, flow velocity 0.5mL/min, λ=254nm) 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.
Embodiment above describes basic principles and main features of the invention and advantages.The technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (7)

1. organic boronic and α, the method for the asymmetric conjugated reaction reaction synthesizing optical activity ketone compounds of alpha, beta-unsaturated ketone, It is characterized in that, reaction equation is as follows:
Specific step is as follows: with α, alpha, beta-unsaturated ketone 1 and organic boronic 2 are raw material, in the chiral four benzo cyclo-octatetraene of catalyst In the presence of class compound and molecular sieve and tert-butyl alcohol magnesium additive, react to obtain ketone chemical combination by asymmetric conjugated reaction Object, wherein R1=phenyl, substituted-phenyl, methyl；R2=phenyl, substituted-phenyl, 2- thienyl, 2- furyl, 1- naphthalene, 2- Naphthalene, ester group, R3=styryl, 2- furyl, 2- benzofuranyl, positive octenyl.
2. organic boronic reacts synthesizing optical activity with the asymmetric conjugated reaction of alpha, beta-unsaturated ketone according to claim 1 The method of ketone compounds, which is characterized in that catalyst four benzo cyclo-octatetraene class compounds of chirality are Cat 1, Cat 2, Cat One of 3 and Cat 4, Cat 1, Cat 2, the specific structure of Cat 3 and Cat 4 are as follows:
。
3. organic boronic reacts synthesizing optical activity with the asymmetric conjugated reaction of alpha, beta-unsaturated ketone according to claim 1 The method of ketone compounds, which is characterized in that R1Selected from Ph, 4-CH3OC6H4、4-BrC6H4Or Me；R2Selected from Ph, 4- CH3OC6H4、4-FC6H4、4-ClC6H4、4-BrC6H4、2-BrC6H4、4-CF3C6H4、4-NO2C6H4, 2- thienyl, 2- furyl, 1- naphthalene, 2- naphthalene or CO2Et； R2It is selected from、、Or。
4. organic boronic reacts synthesizing optical activity with the asymmetric conjugated reaction of alpha, beta-unsaturated ketone according to claim 1 The method of ketone compounds, which is characterized in that the α, alpha, beta-unsaturated ketone 1, organic boronic 2, catalyst, tert-butyl alcohol magnesium mole Than for 1:1.2:0.05:0.05.
5. organic boronic reacts synthesizing optical activity with the asymmetric conjugated reaction of alpha, beta-unsaturated ketone according to claim 1 The method of ketone compounds, which is characterized in that the reaction dissolvent is selected from methyl tertiary butyl ether(MTBE), toluene, methylene chloride, tetrahydro furan It mutters, one of benzotrifluoride, ortho-xylene, 1,2- dichloroethanes, Di Iso Propyl Ether, 1,4- dioxane and acetonitrile.
6. organic boronic reacts synthesizing optical activity with the asymmetric conjugated reaction of alpha, beta-unsaturated ketone according to claim 1 The method of ketone compounds, which is characterized in that reaction temperature is 0 to 25 DEG C.
7. organic boronic reacts synthesizing optical activity with the asymmetric conjugated reaction of alpha, beta-unsaturated ketone according to claim 1 The method of ketone compounds, which is characterized in that entire reaction process needs carry out under nitrogen or argon atmosphere.
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