加氫酰化反應

加氫酰化反應是一種醛分子加成於烯烴或炔烴上，形成酮並增加碳鏈的有機反應。該類反應需要金屬催化劑的參與，且分子內反應優先於分子間反應。與帶有三鍵的炔類底物發生反應，產物為環酮化合物^[1] 。

該反應最早發現於1972年，化學家K.Sakai合成一種前列腺素的路線就應用了此類化學反應^[2]。在該加氫酰化反應中，四氯化錫作為反應試劑，並應用了等當量的威爾金森催化劑的氯仿、乙腈或苯溶液作為催化劑。反應由於脫羰作用生成了等當量的環丙烷。

首個該反應的催化應用於1976年被化學家米勒報道^[3]，該反應中，在威爾金森催化劑與飽和的乙烯溶液的條件下，可將4-戊烯醛轉化為環戊酮。

另一種合適的催化劑為銠的正離子絡合物Rh(dppe)ClO4。

反應機理[編輯]

通常的反應機理為：第一步金屬對醛碳-氫鍵的氧化加成，而後對烯烴的加成，最後發生還原消除。一種可能產生的副反應為，酰基金屬氫化物RCH₂(CO)MH通過中間體RCH₂M(CO)H的脫羧反應，形成烷烴RCH₃與M(CO)。

不對稱加氫酰化[編輯]

第一例加氫酰化的不對稱反應被首先於1983年被化學家James與Young發表（動力學拆分）^[4]^[5]，1989年由Sakai發表了不對稱合成法^[6]^[7]，他們都應用了銠催化劑並使用了手性的二膦配體，如：Me-DuPhos^[8]:

參考文獻[編輯]

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

[2]

[3]

[4]

[5]

[6]

[7]

[8]