加氢酰化反应

加氢酰化反应是一种醛分子加成于烯烃或炔烃上，形成酮并增加碳链的有机反应。该类反应需要金属催化剂的参与，且分子内反应优先于分子间反应。与带有三键的炔类底物发生反应，产物为环酮化合物^[1] 。

该反应最早发现于1972年，化学家K.Sakai合成一种前列腺素的路线就应用了此类化学反应^[2]。在该加氢酰化反应中，四氯化锡作为反应试剂，并应用了等当量的威尔金森催化剂的氯仿、乙腈或苯溶液作为催化剂。反应由于脱羰作用生成了等当量的环丙烷。

首个该反应的催化应用于1976年被化学家米勒报道^[3]，该反应中，在威尔金森催化剂与饱和的乙烯溶液的条件下，可将4-戊烯醛转化为环戊酮。

另一种合适的催化剂为铑的正离子络合物Rh(dppe)ClO4。

通常的反应机理为：第一步金属对醛碳-氢键的氧化加成，而后对烯烃的加成，最后发生还原消除。一种可能产生的副反应为，酰基金属氢化物RCH₂(CO)MH通过中间体RCH₂M(CO)H的脱羧反应，形成烷烃RCH₃与M(CO)。

第一例加氢酰化的不对称反应被首先于1983年被化学家James与Young发表（动力学拆分）^[4]^[5]，1989年由Sakai发表了不对称合成法^[6]^[7]，他们都应用了铑催化剂并使用了手性的二膦配体，如：Me-DuPhos^[8]:

[1]
Transition Metal Catalyzed Alkene and Alkyne Hydroacylation Michael C. Willis Chem. Rev. 2009 doi:10.1021/cr900096x
[2]
Synthetic studies on prostanoids 1 synthesis of methyl 9-oxoprostanoate K. Sakai, J. Ide, O. Oda and N. Nakamura Tetrahedron Letters Volume 13, Issue 13, 1972, Pages 1287-1290 doi:10.1016/S0040-4039(01)84569-X
[3]
Transition-metal-promoted aldehyde-alkene addition reactions Charles F. Lochow, Roy G. Miller J. Am. Chem. Soc., 1976, 98 (5), pp 1281–1283 doi:10.1021/ja00421a050
[4]
The asymmetric cyclisation of substituted pent-4-enals by a chiral rhodium phosphine catalyst Brian R. James and Charles G. Young J. Chem. Soc., Chem. Commun., 1983, 1215 - 1216, doi:10.1039/C39830001215
[5]
Catalytic decarbonylation, hydroacylation, and resolution of racemic pent-4-enals using chiral bis(di-tertiary-phosphine) complexes of rhodium(I) Brian R. James, and Charles G. Young Journal of Organometallic Chemistry Volume 285, Issues 1-3, 16 April 1985, Pages 321-332 doi:10.1016/0022-328X(85)87377-0
[6]
Asymmetric cyclization reactions by Rh(I) with chiral ligands Yukari Tauraa, Masakazu Tanakaa, Kazuhisa Funakoshia and Kiyoshi Sakai Tetrahedron Letters Volume 30, Issue 46, 1989, Pages 6349-6352 {{doi:10.1016/S0040-4039(01)93891-2}}
[7]
Asymmetric cyclization reactions. Cyclization of substituted 4-pentenals into cyclopentanone derivatives by rhodium(I) with chiral ligands Yukari Taura, Masakazu Tanaka, Xiao-Ming Wu, Kazuhisa Funakoshi and Kiyoshi Sakai Tetrahedron Volume 47, Issue 27, 1991, Pages 4879-4888 doi:10.1016/S0040-4020(01)80954-6
[8]
Synthesis of D- and L-Carbocyclic Nucleosides via Rhodium-Catalyzed Asymmetric Hydroacylation as the Key Step Patricia Marce, Yolanda Dıaz, M. Isabel Matheu, and Sergio Castillon Org. Lett., 2008, 10 (21), pp 4735–4738 doi:10.1021/ol801791g

[1] [1]
Transition Metal Catalyzed Alkene and Alkyne Hydroacylation Michael C. Willis Chem. Rev. 2009 doi:10.1021/cr900096x

[2] [2]
Synthetic studies on prostanoids 1 synthesis of methyl 9-oxoprostanoate K. Sakai, J. Ide, O. Oda and N. Nakamura Tetrahedron Letters Volume 13, Issue 13, 1972, Pages 1287-1290 doi:10.1016/S0040-4039(01)84569-X

[3] [3]
Transition-metal-promoted aldehyde-alkene addition reactions Charles F. Lochow, Roy G. Miller J. Am. Chem. Soc., 1976, 98 (5), pp 1281–1283 doi:10.1021/ja00421a050

[4] [4]
The asymmetric cyclisation of substituted pent-4-enals by a chiral rhodium phosphine catalyst Brian R. James and Charles G. Young J. Chem. Soc., Chem. Commun., 1983, 1215 - 1216, doi:10.1039/C39830001215

[5] [5]
Catalytic decarbonylation, hydroacylation, and resolution of racemic pent-4-enals using chiral bis(di-tertiary-phosphine) complexes of rhodium(I) Brian R. James, and Charles G. Young Journal of Organometallic Chemistry Volume 285, Issues 1-3, 16 April 1985, Pages 321-332 doi:10.1016/0022-328X(85)87377-0

[6] [6]
Asymmetric cyclization reactions by Rh(I) with chiral ligands Yukari Tauraa, Masakazu Tanakaa, Kazuhisa Funakoshia and Kiyoshi Sakai Tetrahedron Letters Volume 30, Issue 46, 1989, Pages 6349-6352 {{doi:10.1016/S0040-4039(01)93891-2}}

[7] [7]
Asymmetric cyclization reactions. Cyclization of substituted 4-pentenals into cyclopentanone derivatives by rhodium(I) with chiral ligands Yukari Taura, Masakazu Tanaka, Xiao-Ming Wu, Kazuhisa Funakoshi and Kiyoshi Sakai Tetrahedron Volume 47, Issue 27, 1991, Pages 4879-4888 doi:10.1016/S0040-4020(01)80954-6

[8] [8]
Synthesis of D- and L-Carbocyclic Nucleosides via Rhodium-Catalyzed Asymmetric Hydroacylation as the Key Step Patricia Marce, Yolanda Dıaz, M. Isabel Matheu, and Sergio Castillon Org. Lett., 2008, 10 (21), pp 4735–4738 doi:10.1021/ol801791g

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[4]

[5]

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[8]

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加氢酰化反应

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反应机理

不对称加氢酰化

参考文献