Enantioselective Dicarbofunctionalization of Unactivated Alkenes by Palladium‐Catalyzed Tandem Heck/Suzuki Coupling Reaction. Issue 41 (5th September 2019)

• Record Type: Journal Article
• Authors: Zhang, Zhan‐Ming; Xu, Bing; Wu, Lizuo; Wu, Yuanqi; Qian, Yanyan; Zhou, Lujia; Liu, Yu; Zhang, Junliang
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 41(2019)
• Page Start: 14653
• Page End: 14659
• Publication Date: 2019-09-05
• Subjects: alkenes -- asymmetric catalysis -- cross coupling -- heterocylces -- palladium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201907840
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A highly enantioselective dicarbofunctionalization of unactivated alkenes was implemented by a Pd‐catalyzed asymmetric tandem Heck/Suzuki coupling reaction. This reaction represents the first example of a highly enantioselective intramolecular cyclization/cross‐coupling of olefin‐tethered aryl halides with alkyl‐, alkenyl‐ or arylboronic acids, and provides rapid access to a number of chiral compounds, such as dihydrobenzofurans, indolines, chromanes, and indanes bearing a quaternary stereocenter, in good yields with excellent enantioselectivities. The practicality of this reaction was validated in the modification of biologically complex molecules such as peptides, piperitol, CB2 receptor agonists, etc. Moreover, the synthesis of two enantiomers can be easily realized by simple change in the order of the steps in the coupling sequence. Abstract : The first example of highly enantioselective intramolecular dicarbofunctionalization of unactivated alkenes with alkyl, aryl, or alkenylboronic acids is reported. It provides an efficient synthesis for various chiral benzene‐fused cyclic compounds bearing an all‐carbon quaternary stereocenter, and demonstrates high functional‐group tolerance. The synthesis of a pair of enantiomers was achieved by a change in the order of the steps in the reaction sequence.