Catalyst‐Dependent Rate‐Determining Steps in Regiodivergent Vinylogous Aza‐Morita‐Baylis‐Hillman Reactions with N‐Ts Imines
Catalyst‐Dependent Rate‐Determining Steps in Regiodivergent Vinylogous Aza‐Morita‐Baylis‐Hillman Reactions with N‐Ts Imines
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N-Ts 亚胺区域分散的乙烯 Aza-Morita-Baylis-Hillman 反应中催化剂依赖性速率确定步骤
DOI：
10.1002/ajoc.202100533
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发表时间：
2021
影响因子：
2.7
通讯作者：
Kawabata Takeo
中科院分区：
文献类型：
--
作者：
Gondo Naruhiro;Hyakutake Ryuichi;Fujimura Koki;Ueda Yoshihiro;Nakano Katsuhiko;Tsutsumi Ryosuke;Yamanaka Masahiro;Kawabata Takeo
对乙烯基环戊烯酮进行了催化剂控制的乙烯基氮杂-MBH反应，发现α-加合物只在DABCO催化下得到，而γ-加合物是DMAP-催化下的主要产物。本文报道了DABCO催化的α选择性反应的速率决定步骤是Mannich-型C-−C键形成步骤，而γ-选择性反应的速率决定步骤似乎是β消除步骤。
Catalyst‐controlled vinylogous aza‐MBH reactions of vinylcyclopentenone were performed, and it was found that the α‐adducts were exclusively obtained by DABCO‐catalysis, while the γ‐adducts were the major products by DMAP‐catalysis. We report here that the rate‐determining step of the DABCO‐catalyzed α‐selective reactions is the Mannich‐type C−C bond forming step, while that of the DMAP‐catalyzed γ‐selective reactions seems to be the β‐elimination step.