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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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
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cited_by cdi_FETCH-LOGICAL-a345t-d4869c830aada59babe4a9edc48226b3a5f2d47302e8c5ed37822b5ba44fd9ac3
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container_issue 22
container_start_page 7044
container_title Organic letters
container_volume 20
creator Kondo, Hiroya
Maeno, Mayaka
Sasaki, Kenta
Guo, Ming
Hashimoto, Masaru
Shiro, Motoo
Shibata, Norio
description 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).
doi_str_mv 10.1021/acs.orglett.8b02998
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title Synthesis of Chiral Nonracemic α‑Difluoromethylthio Compounds with Tetrasubstituted Stereogenic Centers via a Palladium-Catalyzed Decarboxylative Asymmetric Allylic Alkylation
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