Catalytic Intramolecular Ketone Alkylation with Olefins by Dual Activation
Catalytic Intramolecular Ketone Alkylation with Olefins by Dual Activation
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DOI：
10.1002/anie.201507741
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发表时间：
2015-12-07
影响因子：
16.6
通讯作者：
Dong, Guangbin
中科院分区：
文献类型：
--
作者：
Lim, Hee Nam;Dong, Guangbin
报道了两种互补的催化分子内酮与未活化烯烃的烷基化反应，导致Conia烯型反应。这种转化是通过酮和烯烃的双重活化实现的，并且是原子经济的，因为不需要化学计量的氧化剂或还原剂。在Kool苯胺催化剂的辅助下，反应条件可以是pH中性和氧化还原中性。因此容许宽范围的官能团。尽管铑催化剂对于五元环的形成是有效的，但是也开发了提供六元环产物的基于铑的系统。
Two complementary methods for catalytic intramolecular ketone alkylation reactions with unactivated olefins, resulting in Conia-ene-type reactions, are reported. The transformations are enabled by dual activation of both the ketone and the olefin and are atom-economical as stoichiometric oxidants or reductants are not required. Assisted by Kool's aniline catalyst, the reaction conditions can be both pH-and redox-neutral. A broad range of functional groups are thus tolerated. Whereas the rhodium catalysts are effective for the formation of five-membered rings, a ruthenium-based system that affords the six-membered ring products was also developed.