Asymmetric Double Hydroxycarbonylation of Alkynes to Chiral Succinic Acids Enabled by Palladium Relay Catalysis. Issue 29 (20th May 2022)

• Record Type: Journal Article
• Authors: Ji, Xiaolei; Shen, Chaoren; Tian, Xinxin; Zhang, Hongru; Ren, Xinyi; Dong, Kaiwu
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 29(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-05-20
• Subjects: Alkynes -- Carbonylation -- Palladium -- Relay Catalysis -- Succinic Acid; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202204156
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A Pd‐catalyzed asymmetric double hydroxycarbonylation of terminal alkynes was developed by using relay catalysis, providing a highly efficient route to chiral succinic acids (41 examples, 76–94 %, 94–99 % ee ). Key to success was the combinatorial use of a Pd precursor with two distinct phosphine ligands in one pot. The synthetic utilities of this protocol were showcased in the facile synthesis of key intermediates for chiral pharmaceuticals. Abstract : By combining two distinct phosphine ligands, a Pd‐catalyzed asymmetric double hydroxycarbonylation of terminal alkynes to chiral succinic acids was achieved in a one‐pot manner. The alkyne carbonylation was dictated by the achiral monophosphine to afford branched acrylic acids, while the resulting intermediates further underwent Pd/chiral bisphosphine‐catalyzed enantioselective hydroxycarbonylation.