Synthesis of Chiral Nonracemic α‑Difluoromethylthio Compounds with Tetrasubstituted Stereogenic Centers via a Palladium-Catalyzed Decarboxylative Asymmetric Allylic Alkylation

The synthesis of chiral, nonracemic difluoromethylthio (SCF2H) compounds that contain a tetrasubstituted stereogenic center is reported. Racemic α-SCF2H-β-ketoallylesters 5 were initially prepared by an electrophilic difluoromethylthiolation of β-ketoallylesters 6, followed by a Pd-catalyzed Tsuji d...

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Bibliographic Details
Published in:Organic letters 2018-11, Vol.20 (22), p.7044-7048
Main Authors: Kondo, Hiroya, Maeno, Mayaka, Sasaki, Kenta, Guo, Ming, Hashimoto, Masaru, Shiro, Motoo, Shibata, Norio
Format: Article
Language:English
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Summary:The synthesis of chiral, nonracemic difluoromethylthio (SCF2H) compounds that contain a tetrasubstituted stereogenic center is reported. Racemic α-SCF2H-β-ketoallylesters 5 were initially prepared by an electrophilic difluoromethylthiolation of β-ketoallylesters 6, followed by a Pd-catalyzed Tsuji decarboxylative asymmetric allylic alkylation (DAAA) to provide a wide variety of chiral, nonracemic α-allyl-α-SCF2H-ketones (4) with high enantiopurity. This strategy can be extended to the enantioselective synthesis of chiral, nonracemic α-allyl-α-trifluoromethylthio­(SCF3)-ketones (7).
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.8b02998