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Asymmetric Synthesis of Tertiary Alcohols and Thiols via Nonstabilized Tertiary ?-Oxy- and ?-Thio-Substituted Organolithium Species.

ABSTRACT: Nonstabilized ?-O-substituted tertiary organolithium species are difficult to generate, and the ?-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 ?-S-organolithium species was enhanced by using a less coordinating solvent and short reaction times.

SUBMITTER: Pulis AP

PROVIDER: S-EPMC5601220 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature

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Asymmetric Synthesis of Tertiary Alcohols and Thiols via Nonstabilized Tertiary α-Oxy- and α-Thio-Substituted Organolithium Species.

Pulis Alexander P AP Varela Ana A Citti Cinzia C Songara Pradip P Leonori Daniele D Aggarwal Varinder K VK

Angewandte Chemie (International ed. in English) 20170807 36

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. ...[more]

PMID: 28783238

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