福山偶聯反應

Fukuyama偶聯反應（福山偶聯反應）

由日本人福山透（Fukuyama Tōru）等在 1998 年發現。是將羧酸及其衍生物轉變為酮的方法之一。反應選擇性高，有機鋅試劑毒性較小，活性較低，因此反應條件溫和，許多官能團（如醛、酮、氯代芳烴、硫醚等）不受影響。^[2] 反應到酮停止，不再繼續將酮還原為醇。

反應機理

{\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偶聯

^ 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.