Asymmetric Synthesis of Tertiary Alcohols and Thiols via Nonstabilized Tertiary α‐Oxy‐ and α‐Thio‐Substituted Organolithium Species. Issue 36 (7th August 2017)

• Record Type: Journal Article
• Authors: Pulis, Alexander P.; Varela, Ana; Citti, Cinzia; Songara, Pradip; Leonori, Daniele; Aggarwal, Varinder K.
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 36(2017)
• Page Start: 10835
• Page End: 10839
• Publication Date: 2017-08-07
• Subjects: chiral organolithium species -- IR spectroscopy -- tertiary alcohols -- tertiary thiols; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201706722
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Nonstabilized α‐O‐substituted tertiary organolithium species are difficult to generate, and the α‐S‐substituted analogues are configurationally unstable. We now report that they can both be generated easily and trapped with a range of electrophiles with high enantioselectivity, providing ready access to a range of enantioenriched tertiary alcohols and thiols. The configurational stability of the α‐S‐organolithium species was enhanced by using a less coordinating solvent and short reaction times. Abstract : Enantioenriched, nonstabilized, tertiary organolithium species with α‐O and α‐S substitution are of remarkable configurational stability (R, R′=alkyl). They can thus be trapped with a broad range of electrophiles to generate tertiary alcohol and tertiary thiol derivatives with excellent enantioselectivity.