福山偶联反应

Fukuyama偶联反应（福山偶联反应）

由日本人福山透（Fukuyama Tōru）等在 1998 年发现。是将羧酸及其衍生物转变为酮的方法之一。反应选择性高，有机锌试剂毒性较小，活性较低，因此反应条件温和，许多官能团（如醛、酮、氯代芳烃、硫醚等）不受影响。^[2] 反应到酮停止，不再继续将酮还原为醇。

反应机理

{\rm {\ RC(O)SEt\ +}}

“

{\rm {\ Pd}}

”

{\rm {\ \rightarrow RC(O)\!-\!Pd(II)\!-\!SEt}}

{\rm {\ RC(O)\!-\!Pd(II)\!-\!SEt+R'ZnI\rightarrow RC(O)\!-\!Pd(II)\!-\!R'+EtSZnI}}

{\rm {\ RC(O)\!-\!Pd(II)\!-\!R'\rightarrow RC(O)R'+}}

“

{\rm {\ Pd}}

1、生物素的合成：^[3]

生物素合成 Fukuyama偶联

^ Hidetoshi Tokuyama, Satoshi Yokoshima, Tohru Yamashita and Tohru Fukuyama. A novel ketone synthesis by a palladium-catalyzed reaction of thiol esters and organozinc reagents. Tetrahedron Letters. 1998, 39 (20): 3189–3192. doi:10.1016/S0040-4039(98)00456-0.
^ Yoshikazu Mori, Masahiko Seki (2007). "Synthesis of Multi-functionalized Ketones through the Fukuyama Coupling Reaction Catalyzed by Pearlman's Catalyst: Preparation of Ethyl 6-Oxotridecanoate". Org. Synth.; Coll. Vol. 84: 285–294.
^ Toshiaki Shimizu and Masahiko S. Facile synthesis of (+)-biotin via Fukuyama coupling reaction. Tetrahedron Letters. 2000, 41 (26): 5099–5101. doi:10.1016/S0040-4039(98)00456-0.