Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 37, Pages 20424-20429Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202106871
Keywords
alkyne; arylation; axial chirality; C-H activation; desymmetrization
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Funding
- NSFC [21525208]
- SNNU
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A novel method for the construction of biaryls with central and axial chirality through rhodium-catalyzed 1:2 coupling of diarylphosphinic amides and diarylacetylenes has been reported. This new method shows better chemoselectivity compared to previously explored Miura-Satoh type 1:2 coupling, and proceeds under mild conditions using a rare arylating reagent.
C-H bond activation has been established as an attractive strategy to access axially chiral biaryls, and the most straightforward method is direct C-H arylation of arenes. However, the arylating source has been limited to several classes of reactive and bulky reagents. Reported herein is rhodium-catalyzed 1:2 coupling of diarylphosphinic amides and diarylacetylenes for enantio- and diastereoselective construction of biaryls with both central and axial chirality. This twofold C-H activation reaction stays contrast to the previously explored Miura-Satoh type 1:2 coupling of arenes and alkynes in terms of chemoselectivity and proceeded under mild conditions with the alkyne acting as a rare arylating reagent. Both C-H activation events are stereo-determining and are under catalyst control, with the 2(nd) C-H activation being diastereo-determining in a remote fashion. Analysis of the stereochemistry of the major and side products suggests moderate enantioselectivity of the initial C-H activation-desymmetrization process. However, the minor (R) rhodium vinyl intermediate is consumed more readily in undesired protonolysis, eventually resulting in high enantio- and diastereoselectivity of the major product.
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