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

Alexander P. Pulis; Ana Varela; Cinzia Citti; Pradip Songara; Daniele Leonori; Varinder  K Aggarwal

doi:10.1002/anie.201706722

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

Alexander P. Pulis, Ana Varela, Cinzia Citti, Pradip Songara, Daniele Leonori, Varinder K Aggarwal

University of Bristol

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	10835-10839
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	36
Early online date	7 Aug 2017
DOIs	https://doi.org/10.1002/anie.201706722
Publication status	Published - 23 Aug 2017

Keywords

chiral organolithium species
IR spectroscopy
tertiary alcohols
tertiary thiols

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10.1002/anie.201706722Licence: Unspecified

CCDC 1557928: Experimental Crystal Structure Determination
Pulis, A. (Contributor), Varela, A. (Contributor), Citti, C. (Contributor), Songara, P. (Contributor), Leonori, D. (Contributor) & Aggarwal, V. K. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1p94rw, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p94rw&sid=DataCite
Dataset
CCDC 1557929: Experimental Crystal Structure Determination
Pulis, A. (Contributor), Varela, A. (Contributor), Citti, C. (Contributor), Songara, P. (Contributor), Leonori, D. (Contributor) & Aggarwal, V. K. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1p94sx, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p94sx&sid=DataCite
Dataset

Cite this

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title = "Asymmetric Synthesis of Tertiary Alcohols and Thiols via Nonstabilized Tertiary α-Oxy- and α-Thio-Substituted Organolithium Species",

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.",

keywords = "chiral organolithium species, IR spectroscopy, tertiary alcohols, tertiary thiols",

author = "Pulis, {Alexander P.} and Ana Varela and Cinzia Citti and Pradip Songara and Daniele Leonori and Aggarwal, {Varinder K}",

year = "2017",

month = aug,

day = "23",

doi = "10.1002/anie.201706722",

language = "English",

volume = "56",

pages = "10835--10839",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley & Sons Ltd",

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TY - JOUR

T1 - Asymmetric Synthesis of Tertiary Alcohols and Thiols via Nonstabilized Tertiary α-Oxy- and α-Thio-Substituted Organolithium Species

AU - Pulis, Alexander P.

AU - Varela, Ana

AU - Citti, Cinzia

AU - Songara, Pradip

AU - Leonori, Daniele

AU - Aggarwal, Varinder K

PY - 2017/8/23

Y1 - 2017/8/23

N2 - 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.

AB - 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.

KW - chiral organolithium species

KW - IR spectroscopy

KW - tertiary alcohols

KW - tertiary thiols

U2 - 10.1002/anie.201706722

DO - 10.1002/anie.201706722

M3 - Article

AN - SCOPUS:85028090681

SN - 1433-7851

VL - 56

SP - 10835

EP - 10839

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 36

ER -

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

Abstract

Keywords

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Datasets

CCDC 1557928: Experimental Crystal Structure Determination

CCDC 1557929: Experimental Crystal Structure Determination

Cite this