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Title: Enantiodivergent Pd-catalyzed C–C bond formation enabled through ligand parameterization
Despite the enormous potential for the use of stereospecific cross-coupling reactions to rationally manipulate the three-dimensional structure of organic molecules, the factors that control the transfer of stereochemistry in these reactions remain poorly understood. Here we report a mechanistic and synthetic investigation into the use of enantioenriched alkylboron nucleophiles in stereospecific Pd-catalyzed Suzuki cross-coupling reactions. By developing a suite of molecular descriptors of phosphine ligands, we could apply predictive statistical models to select or design distinct ligands that respectively promoted stereoinvertive and stereoretentive cross-coupling reactions. Stereodefined branched structures were thereby accessed through the predictable manipulation of absolute stereochemistry, and a general model for the mechanism of alkylboron transmetallation was proposed.  more » « less
Award ID(s):
1763436
PAR ID:
10079146
Author(s) / Creator(s):
; ; ; ; ;
Publisher / Repository:
American Association for the Advancement of Science (AAAS)
Date Published:
Journal Name:
Science
Volume:
362
Issue:
6415
ISSN:
0036-8075
Page Range / eLocation ID:
p. 670-674
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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