Stereoselective Cyclopropanation of 1,1-Diborylalkenes via Palladium-Catalyzed (Trimethylsilyl)diazomethane Insertion

Palladium catalyzes the cyclopropanation of 2-substituted 1,1-diborylalkenes with (trimethylsilyl)­diazomethane. The relative stereoselectivity is controlled via a carbene insertion sequence generating an exclusive anti conformation between the R and SiMe3 substituents. Mixed 1,1-diborylalkenes also...

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Bibliographic Details
Published in:Organic letters 2022-07, Vol.24 (27), p.4949-4953
Main Authors: Salvado, Oriol, Dominguez-Molano, Paula, Fernández, Elena
Format: Article
Language:English
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Letter
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Summary:Palladium catalyzes the cyclopropanation of 2-substituted 1,1-diborylalkenes with (trimethylsilyl)­diazomethane. The relative stereoselectivity is controlled via a carbene insertion sequence generating an exclusive anti conformation between the R and SiMe3 substituents. Mixed 1,1-diborylalkenes also contributed to the formation of stereoselective B, B, Si-cyclopropanes. Orthogonal activation with NaO t Bu gives protodeborylation preferentially on the boron moiety syn to the aryl group. Further oxidation gives access to polyfunctional cyclopropyl alcohols with controlled enantioselectivity when chiral boryl motifs are involved.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.2c01885