脯氨酸衍生物催化蒽酮与硝基烯烃的不对称Michael加成反应
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摘要
目的筛选出适用于β-硝基烯的不对称Michael加成反应的有机催化剂体系。方法设计、合成脯氨酸衍生物催化剂,应用于反式硝基苯乙烯和蒽酮的不对称Michael加成反应。考察溶剂、温度、催化剂用量等因素对反应立体选择性的影响。结果最佳的催化剂体系为:10 mol%的催化剂1b,甲苯为溶剂,室温反应。结论将筛选出的催化剂体系用于不同取代基的反式β-硝基烯烃和蒽酮的不对称Michael加成反应,得到了很好的产率(88%~98%)和最高达66%ee的立体选择性。
Objective To screen out the organiccatalyst system for the asymmetric Michael addition reaction of β-nitroene. Methods Proline Derivative as organocatalysts were applied in asymmetric Michael addition reaction of anthrone with different nitroalkenes. The effect of solvent,temperature and catalyst loading were investigated. Results The optimized conditions were confirmed to include toluene as the solvent with a 10% catalyst of 1 b at room temperature. Conclusion The screened catalyst system is applied to the asymmetric Michael addition reaction of anthrone with 10 nitroalkenes,the products were obtained in 88% ~ 98% yield and with up to 66% ee.
Objective To screen out the organiccatalyst system for the asymmetric Michael addition reaction of β-nitroene. Methods Proline Derivative as organocatalysts were applied in asymmetric Michael addition reaction of anthrone with different nitroalkenes. The effect of solvent,temperature and catalyst loading were investigated. Results The optimized conditions were confirmed to include toluene as the solvent with a 10% catalyst of 1 b at room temperature. Conclusion The screened catalyst system is applied to the asymmetric Michael addition reaction of anthrone with 10 nitroalkenes,the products were obtained in 88% ~ 98% yield and with up to 66% ee.
引文
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[9]张天一,年文霞,金瑛.有机催化蒽酮与β-硝基烯烃的不对称Michael加成反应[J].应用化学,2015,32(4):422-427.
[10]LIST B,POJARLIEV P,MARTIN H J.Efficient prolinecatalyzed Michael additions of unmodified ketones to nitro olefins[J].Org Lett,2001,3(16):2423-2425.
[11]ISHII T,FUJIOKA S,SEKIGUCHI Y,et al.A new class of chiral pyrrolidine-pyridine conjugate base catalysts for use in asymmetric Michael addition reactions[J].J Am Chem Soc,2004,126(31):9558-9559.
[12]LUO S Z,MI X,ZHANG L,et al.Functionalized chiral ionic liquids as highly efficient asymmetric organocatalysts for Michael addition to nitroolefins[J].Angew Chem Int Ed Engl,2006,45(19):3093-3097.
[13]CAO C L,YE M C,SUN X L,et al.Pyrrolidine-Thiourea as a Bifunctional organocatalyst:Highly Enantioselective Michael Addition of Cyclohexanone to Nitroolefins Pyrrolidine-thiourea as a bifunctional organocatalyst:highly enantioselective Michael addition of cyclohexanone to nitroolefins[J].Org Lett,2006,8(14):2901-2904.
[14]SATHISH K,KUMAR REDDY G P,MAINKAR P,et al.Synthesis of the‘southern’tripeptide of Cyclomarins A and C having novel anti-tuberculocidal mode of action[J].Tetrahedron Asymmetr,2011,22(14/15):1568-1573.
[15]AQARWAL J,PEDDINTI R K.Glucosamine-based primary amines as organocatalysts for the asymmetric aldol reaction[J].J Org Chem,2011,79(6):3502-3505.
[2]WEI S W,YALAOV D A,TSOGOEVA S B,et al.New highly enantioselective thiourea-based bifunctional organocatalysts for nitro-Michael addition reactions[J].Catal Today,2007,121(1):151-157.
[3]BALLINI R,BOSICA G,FIORINI D,et al.Acyclic a-nitro ketones:a versatile class of a-functionalized ketones in organic synthesis[J].Tetrahedron,2005,61(38):8971-8993.
[4]SAHA S,SETH S,MOORTHY J N,et al.Chem Inform abstract:Functionalized proline with double hydrogen bonding potential:highly enantioselective Michael addition of carbonyl compounds toβ-nitrostyrenes in brine[J].Tetrahedron Lett,2010,51(40):5281-5286.
[5]BURKETT B A,KANE-BARBER J M,O'REILLY R J,et al.Polymer-supported thiobenzophenone:a self-indicating traceless‘catch and release’linker for the synthesis of isothiocyanates[J].Tetrahedron Lett,2007,48(31):5355-5358.
[6]LBA A N,BRAVO N,MOYANO A,et al.Chem Inform abstract:Enantioselective addition of anthrones toα,β-unsaturated aldehydes Short communication[J].Tetrahedron Lett,2009,50(25):3067-3069.
[7]LIAO Y H,ZHANG H,WU Z J,et al.Enantioselective Michael addition of anthrone to nitroalkenes catalyzed by bifunctional thiourea-tertiary amines[J].Tetrahedron Asymmetr,2009,20(20):2397-2402.
[8]何天雄,伍新燕.蒽酮与β-硝基苯乙烯的不对称Michael加成反应[J].有机化学,2010,30(9):1400-1404.
[9]张天一,年文霞,金瑛.有机催化蒽酮与β-硝基烯烃的不对称Michael加成反应[J].应用化学,2015,32(4):422-427.
[10]LIST B,POJARLIEV P,MARTIN H J.Efficient prolinecatalyzed Michael additions of unmodified ketones to nitro olefins[J].Org Lett,2001,3(16):2423-2425.
[11]ISHII T,FUJIOKA S,SEKIGUCHI Y,et al.A new class of chiral pyrrolidine-pyridine conjugate base catalysts for use in asymmetric Michael addition reactions[J].J Am Chem Soc,2004,126(31):9558-9559.
[12]LUO S Z,MI X,ZHANG L,et al.Functionalized chiral ionic liquids as highly efficient asymmetric organocatalysts for Michael addition to nitroolefins[J].Angew Chem Int Ed Engl,2006,45(19):3093-3097.
[13]CAO C L,YE M C,SUN X L,et al.Pyrrolidine-Thiourea as a Bifunctional organocatalyst:Highly Enantioselective Michael Addition of Cyclohexanone to Nitroolefins Pyrrolidine-thiourea as a bifunctional organocatalyst:highly enantioselective Michael addition of cyclohexanone to nitroolefins[J].Org Lett,2006,8(14):2901-2904.
[14]SATHISH K,KUMAR REDDY G P,MAINKAR P,et al.Synthesis of the‘southern’tripeptide of Cyclomarins A and C having novel anti-tuberculocidal mode of action[J].Tetrahedron Asymmetr,2011,22(14/15):1568-1573.
[15]AQARWAL J,PEDDINTI R K.Glucosamine-based primary amines as organocatalysts for the asymmetric aldol reaction[J].J Org Chem,2011,79(6):3502-3505.
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