叔膦或叔胺催化的活化烯烃的环加成反应以及酮亚胺的不对称aza-Morita-Baylis-Hillman反应的研究
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摘要
近年来,手性膦广泛应用于不对称有机催化当中,成为有机催化的一个热点。本论文的工作主要从以下两个方面展开：(1)手性双官能团膦催化的MBH产物碳酸酯,联烯酸酯和活化二烯的环加成反应,合成一类官能团化的五元或六元环化合物；(2)叔膦或叔胺催化的基于靛红骨架酮亚胺与丁烯酮的不对称aza-Morita-Baylis-Hillman (aza-MBH)反应,合成光学纯的3-氨基-2-吲哚酮衍生物,具体可分为以下四个部分：
第一部分：PPh3和SPTS催化的活化联烯与邻羟基苯甲酰甲酸乙酯的[4+2]环加成反应。发展了叔膦催化的联烯酸酯与邻羟基苯甲酰甲酸乙酯的[4+2]环加成反应,能以良好到优秀的总产率得到含有季碳中心色满衍生物；发现了SPTS可以催化联烯砜与邻羟基苯甲酰甲酸乙酯的[4+2]环加成反应,能以中等收率得到单一异构体的色满类化合物。
第二部分：手性膦催化的MBH产物碳酸酯的不对称环加成反应。(1)基于我们小组之前的工作,报道了手性双官能团膦-硫脲催化剂催化的MBH产物碳酸酯与缺电子烯烃的不对称[3+2]环加成反应,能以中等收率和优秀的ee值以及单一异构体得到官能团化的五元环产物；(2)报到了基于联萘骨架的双官能团膦催化的MBH产物碳酸酯与α,β-不饱和酮的[4+1]环加成反应,能以较好的结果合成具有两个临近的季碳中心的螺吲哚酮衍生物。
第三部分：叔膦或叔胺催化的基于靛红骨架的酮亚胺与丁烯酮(MVK)的不对称aza-MBH反应。首次报道了叔膦或叔胺催化的酮亚胺与MVK的不对称aza-MBH反应,能够以优秀的产率和优秀的对映选择性得到具有光学纯的3-氨基-2-吲哚酮类衍生物。进一步机理研究表明,该反应不存在非线性效应。
第四部分：叔膦催化的活化二烯烃与缺电子烯烃的不对称[4+2]串联环化反应。首次报道了叔膦催化的基于靛红骨架二氰基烯烃与活化二烯烃的不对称形式上[4+2]串联环化反应,能以良好到优秀的收率和优秀的ee值以及优秀的非对映选择性得到多手性中心的螺环化合物。该反应主要是经过Rauhut-Currier/Michael/Rauhut-Currier过程实现的,并且我们也对产物进行转化,得到手性保持的多环化合物。
Recently, chiral phosphines are widely used in catalytic asymmetric organocatalysis, and become an active area in asymmetric organocatalysis. This dissertation mainly focuses on:(1) tertiary phosphine-catalyzed annulations of activated allenes, MBH carbonates and activated dienes, affording functionalized five-memberd or six-memberd compounds;(2) chiral phosphine or amine-catalyzed asymmetric aza-Morita-Baylis-Hillman (aza-MBH) reaction, giving the optically active3-amino-2-oxindoles bearing quaternary stereogenic centers. The dissertation is concretely divided into four parts:
Part I:Tertiary phosphine and SPTS-catalyzed [4+2] annulations of activated allenes with ethyl2-(2-hydroxyaryl)-2-oxoacetates. A fairly efficient [4+2] annulation reaction of allenic ester or allenylsulfone with ethyl2-(2-hydroxyaryl)-2-oxoacetates catalyzed by tertiary phosphine and SPTS, respectively, has been developed, which provides an easy access to the synthesis of the corresponding quaternary carbon centered chroman derivatives under mild reaction conditions in moderate to good yields.
Part II:Chiral phosphine-catalyzed asymmetric annulations of MBH carbonates.(1) Based on our previous work, a fairly efficient [3+2] annulation reaction of2-arylideneindane-1,3-diones with MBH carbonates catalyzed by bifunctional thiourea-phosphine catalysts has been disclosed, giving the functionalized cyclopentenes under mild reaction conditions in moderate to good yields (up to75%), with high diastereoselectivities (up to>99:1) and enantioselectivities (up to98%);(2) The asymmetric [4+1] annulations of a,(3-unsaturated ketones with MBH carbonates catalyzed by bifunctional thiourea-phosphine catalyst derived from an axially chiral binaphthyl scaffold has been developed, producing spirooxindoles containing two adjacent tertiary stereocenters with a good outcome.
Part III:Chiral amine-or phosphine-catalyzed asymmetric aza-MBH reaction of ketimines derived from isatin with methyl vinyl ketone (MVK). The asymmetric aza-MBH reaction of isatin-derived N-Boc ketimines with MVK catalyzed by chiral amine and phosphine has been developed for the first time, which provides an highly efficient and enantioselective synthesis of3-amino-2-oxindoles bearing quaternary stereogenic center. Further mechanistic investigations elucidate that no non-linear effect was observed in this reaction.
Part IV:Phosphine-catalyzed asymmetric formal [4+2] tandem cyclization of activated dienes with isatylidene malononitriles. The first highly enantioselective formal [4+2] tandem cyclization between isatylidene malononitriles and activated dienes catalyzed by bifunctional chiral phosphine catalysts has been disclosed, yielding the multi-stereogenic spirocyclic oxindoles in high yields along with excellent enantioselectivities and diastereoselectivities. This reaction is proposed to proceed via Rauhut-Currier/Michael/Rauhut-Currier reaction sequence. Sequences of transformations are also conducted for synthesis of polycyclic compound with the same enantiomeric excess.
第一部分：PPh3和SPTS催化的活化联烯与邻羟基苯甲酰甲酸乙酯的[4+2]环加成反应。发展了叔膦催化的联烯酸酯与邻羟基苯甲酰甲酸乙酯的[4+2]环加成反应,能以良好到优秀的总产率得到含有季碳中心色满衍生物；发现了SPTS可以催化联烯砜与邻羟基苯甲酰甲酸乙酯的[4+2]环加成反应,能以中等收率得到单一异构体的色满类化合物。
第二部分：手性膦催化的MBH产物碳酸酯的不对称环加成反应。(1)基于我们小组之前的工作,报道了手性双官能团膦-硫脲催化剂催化的MBH产物碳酸酯与缺电子烯烃的不对称[3+2]环加成反应,能以中等收率和优秀的ee值以及单一异构体得到官能团化的五元环产物；(2)报到了基于联萘骨架的双官能团膦催化的MBH产物碳酸酯与α,β-不饱和酮的[4+1]环加成反应,能以较好的结果合成具有两个临近的季碳中心的螺吲哚酮衍生物。
第三部分：叔膦或叔胺催化的基于靛红骨架的酮亚胺与丁烯酮(MVK)的不对称aza-MBH反应。首次报道了叔膦或叔胺催化的酮亚胺与MVK的不对称aza-MBH反应,能够以优秀的产率和优秀的对映选择性得到具有光学纯的3-氨基-2-吲哚酮类衍生物。进一步机理研究表明,该反应不存在非线性效应。
第四部分：叔膦催化的活化二烯烃与缺电子烯烃的不对称[4+2]串联环化反应。首次报道了叔膦催化的基于靛红骨架二氰基烯烃与活化二烯烃的不对称形式上[4+2]串联环化反应,能以良好到优秀的收率和优秀的ee值以及优秀的非对映选择性得到多手性中心的螺环化合物。该反应主要是经过Rauhut-Currier/Michael/Rauhut-Currier过程实现的,并且我们也对产物进行转化,得到手性保持的多环化合物。
Recently, chiral phosphines are widely used in catalytic asymmetric organocatalysis, and become an active area in asymmetric organocatalysis. This dissertation mainly focuses on:(1) tertiary phosphine-catalyzed annulations of activated allenes, MBH carbonates and activated dienes, affording functionalized five-memberd or six-memberd compounds;(2) chiral phosphine or amine-catalyzed asymmetric aza-Morita-Baylis-Hillman (aza-MBH) reaction, giving the optically active3-amino-2-oxindoles bearing quaternary stereogenic centers. The dissertation is concretely divided into four parts:
Part I:Tertiary phosphine and SPTS-catalyzed [4+2] annulations of activated allenes with ethyl2-(2-hydroxyaryl)-2-oxoacetates. A fairly efficient [4+2] annulation reaction of allenic ester or allenylsulfone with ethyl2-(2-hydroxyaryl)-2-oxoacetates catalyzed by tertiary phosphine and SPTS, respectively, has been developed, which provides an easy access to the synthesis of the corresponding quaternary carbon centered chroman derivatives under mild reaction conditions in moderate to good yields.
Part II:Chiral phosphine-catalyzed asymmetric annulations of MBH carbonates.(1) Based on our previous work, a fairly efficient [3+2] annulation reaction of2-arylideneindane-1,3-diones with MBH carbonates catalyzed by bifunctional thiourea-phosphine catalysts has been disclosed, giving the functionalized cyclopentenes under mild reaction conditions in moderate to good yields (up to75%), with high diastereoselectivities (up to>99:1) and enantioselectivities (up to98%);(2) The asymmetric [4+1] annulations of a,(3-unsaturated ketones with MBH carbonates catalyzed by bifunctional thiourea-phosphine catalyst derived from an axially chiral binaphthyl scaffold has been developed, producing spirooxindoles containing two adjacent tertiary stereocenters with a good outcome.
Part III:Chiral amine-or phosphine-catalyzed asymmetric aza-MBH reaction of ketimines derived from isatin with methyl vinyl ketone (MVK). The asymmetric aza-MBH reaction of isatin-derived N-Boc ketimines with MVK catalyzed by chiral amine and phosphine has been developed for the first time, which provides an highly efficient and enantioselective synthesis of3-amino-2-oxindoles bearing quaternary stereogenic center. Further mechanistic investigations elucidate that no non-linear effect was observed in this reaction.
Part IV:Phosphine-catalyzed asymmetric formal [4+2] tandem cyclization of activated dienes with isatylidene malononitriles. The first highly enantioselective formal [4+2] tandem cyclization between isatylidene malononitriles and activated dienes catalyzed by bifunctional chiral phosphine catalysts has been disclosed, yielding the multi-stereogenic spirocyclic oxindoles in high yields along with excellent enantioselectivities and diastereoselectivities. This reaction is proposed to proceed via Rauhut-Currier/Michael/Rauhut-Currier reaction sequence. Sequences of transformations are also conducted for synthesis of polycyclic compound with the same enantiomeric excess.
引文
[1]林国强,李月明,陈耀全,孙兴文,陈新滋 手性合成-不对称反应及其应用,第四版,科学出版社,2010,p.1-63.
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