Enantio- and Diastereoselective Suzuki-Miyaura Coupling with Racemic Bicycles

24 May 2019, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Herein we describe a rhodium-catalyzed enantio- and diastereoselective Suzuki-Miyaura cross-coupling between racemic fused bicyclic allylic chlorides and boronic acids. The highly stereoselective transformation allows for the coupling of aryl-, heteroaryl- and vinyl boronic acids and gives access to functionalized bicyclic cyclopentenes which can be converted to other five-membered ring scaffolds with up to five contiguous stereocenters. Preliminary mechanistic studies suggest that these reactions occur with overall retention of the relative stereochemistry and is enantioconvergent for pseudo-symmetric allylic chloride starting materials. In addition, a bicyclic allylic chloride starting material without pseudo-symmetry undergoes a highly enantioselective regiodivergent reaction.


Asymmetric Catalysis
boronic acids
Suzuki-Miyaura coupling

Supplementary materials

SI bicycle cross-coupling


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