Visible-Light-Driven Alkyne Hydro-/Carbocarboxylation Using CO2 via Iridium/Cobalt Dual Catalysis for Divergent Heterocycle Synthesis
Visible-Light-Driven Alkyne Hydro-/Carbocarboxylation Using CO2 via Iridium/Cobalt Dual Catalysis for Divergent Heterocycle Synthesis
复制标题
DOI：
10.1021/jacs.8b01561
复制
发表时间：
2018-04-18
影响因子：
15
通讯作者：
Wu, Jie
中科院分区：
文献类型：
--
作者：
Hou, Jing;Ee, Aloysius;Wu, Jie
我们在此提出了第一个可见光驱动的加氢羧化以及碳羧化的炔使用二氧化碳通过铱/钴双催化。这样的转化提供了从容易获得的炔在一锅法中获得各种药学上重要的杂环的途径。香豆素，2-喹诺酮，和2-苯并氧-epinones直接访问通过一锅炔加氢羧化/烯烃异构化/cydization序列中的Ir光催化剂起到双重作用，以促进单电子转移在炔加氢羧化和能量转移在随后的烯烃异构化。此外，前所未有的钴羧化/芳基迁移级联使得炔双官能化能够高效地引入γ-羟基丁烯内酯。我们期望这种级联策略将激发炔和烯烃双官能化的新观点。
We present herein the first visible-light-driven hydrocarboxylation as well as carbocarboxylation of alkynes using CO2 via an iridium/cobalt dual catalysis. Such transformations provide access to various pharmaceutically important heterocycles in a one-pot procedure from readily available alkynes. Coumarins, 2-quinolones, and 2-benzox-epinones were directly accessed through a one-pot alkyne hydrocarboxylation/alkene isomerization/cydization sequence in which the Ir photocatalyst serves a dual role to promote single-electron transfer in alkyne hydrocarboxylation and energy transfer in the subsequent alkene isomerization. Moreover, an unprecedented cobalt carboxylation/aryl migration cascade enables alkyne difunctionalization to introduce gamma-hydroxybutenolides with high efficiency. We expect that this cascade strategy will inspire new perspectives for alkyne and alkene difunctionalization.