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Visible-Light-Driven Alkyne Hydro-/Carbocarboxylation Using CO2 via Iridium/Cobalt Dual Catalysis for Divergent Heterocycle Synthesis
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-03-29 , DOI: 10.1021/jacs.8b01561
Jing Hou 1 , Aloysius Ee 1 , Wei Feng 1 , Jin-Hui Xu 1 , Yu Zhao 1 , Jie Wu 1
Affiliation  

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-benzoxepinones were directly accessed through a one-pot alkyne hydrocarboxylation/alkene isomerization/cyclization 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/acyl migration cascade enables alkyne difunctionalization to introduce γ-hydroxybutenolides with high efficiency. We expect that this cascade strategy will inspire new perspectives for alkyne and alkene difunctionalization.

中文翻译:

可见光驱动炔烃加氢/羧基化,通过铱/钴双催化使用 CO2 进行发散杂环合成

我们在此展示了第一个可见光驱动的烃羧化以及通过铱/钴双催化使用 CO2 的炔烃的羧化。这种转化提供了通过一锅法从容易获得的炔烃获得各种药学上重要的杂环的途径。通过一锅炔烃加氢羧化/烯烃异构化/环化序列直接获得香豆素、2-喹诺酮和 2-苯并氧杂环酮,其中 Ir 光催化剂起到双重作用,促进炔烃加氢羧化中的单电子转移和随后的能量转移烯烃异构化。此外,前所未有的钴羧化/酰基迁移级联使炔双官能化能够高效引入γ-羟基丁烯内酯。
更新日期:2018-03-29
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