Details

Autor(en) / Beteiligte

• Chen, Xiao‐Wang
• Yue, Jun‐Ping
• Wang, Kuai
• Gui, Yong‐Yuan
• Niu, Ya‐Nan
• Liu, Jie
• Ran, Chuan‐Kun
• Kong, Wangqing
• Zhou, Wen‐Jun
• Yu, Da‐Gang

Titel

Nickel‐Catalyzed Asymmetric Reductive Carbo‐Carboxylation of Alkenes with CO2

Ist Teil von

• Angewandte Chemie International Edition, 2021-06, Vol.60 (25), p.14068-14075

Auflage

International ed. in English

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2021

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Reductive carboxylation of organo (pseudo)halides with CO2 is a powerful method to provide carboxylic acids quickly. Notably, the catalytic reductive carbo‐carboxylation of unsaturated hydrocarbons via CO2 fixation is a highly challenging but desirable approach for structurally diverse carboxylic acids. There are only a few reports and no examples of alkenes via transition metal catalysis. We report the first asymmetric reductive carbo‐carboxylation of alkenes with CO2 via nickel catalysis. A variety of aryl (pseudo)halides, such as aryl bromides, aryl triflates and inert aryl chlorides of particular note, undergo the reaction smoothly to give important oxindole‐3‐acetic acid derivatives bearing a C3‐quaternary stereocenter. This transformation features mild reaction conditions, wide substrate scope, facile scalability, good to excellent chemo‐, regio‐ and enantioselectivities. The method highlights the formal synthesis of (−)‐Esermethole, (−)‐Physostigmine and (−)‐Physovenine, and the total synthesis of (−)‐Debromoflustramide B, (−)‐Debromoflustramine B and (+)‐Coixspirolactam A; thereby, opening an avenue for the total synthesis of chiral natural products with CO2. A strategy is presented for nickel‐ catalyzed asymmetric reductive carbo‐carboxylation of alkenes with CO2. A variety of aryl (pseudo)halides react to produce oxindole‐3‐acetic acid derivatives bearing a C3‐quaternary stereocenter. Notably, synthesis of a range of bioactive pyrroloindolines was achieved.