Asymmetric Synthesis of Secondary and Tertiary Propargylic Alcohols by Umpolung of Acetylenic Sulfones and ortho-Sulfinyl Carbanions

The generation of diastereomerically enriched secondary benzyl propargyl alcohols by the asymmetric addition of ortho-sulfinylbenzyl carbanions to sulfonylacetylene derivatives via formation of a Csp–Csp3 bond is described. This reaction proceeds through an unusual α-attack (anti-Michael addition) o...

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Bibliographic Details
Published in:Journal of organic chemistry 2018-02, Vol.83 (4), p.1940-1947
Main Authors: Rodríguez, Ricardo I, Ramírez, Elsie, Yuste, Francisco, Sánchez-Obregón, Rubén, Alemán, José
Format: Article
Language:English
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Summary:The generation of diastereomerically enriched secondary benzyl propargyl alcohols by the asymmetric addition of ortho-sulfinylbenzyl carbanions to sulfonylacetylene derivatives via formation of a Csp–Csp3 bond is described. This reaction proceeds through an unusual α-attack (anti-Michael addition) of the ortho-sulfinylbenzyl carbanions, followed by elimination of the arylsulfonyl moiety. The scope of this alkynylation reaction is also discussed. Moreover, the development of a new approach for the synthesis of optically active tertiary benzylpropargyl alcohols is described, discussing the possible stereocourse of the reaction so as the influence of the ether 18-crown-6 and steric importance of acetylenic substituent.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.7b02887