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

Alex Pulis; Ana Varela; Cinzia Citti; Pradip Songara; Daniele Leonori; Varinder Aggarwal

doi:10.1002/anie.201706722

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

Alex Pulis
, Ana Varela
, Cinzia Citti
, Pradip Songara
, Daniele Leonori
, Varinder Aggarwal

Research output: Contribution to journal › Article (Academic Journal) › peer-review

18 Citations (Scopus)

579 Downloads (Pure)

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 - 28 Aug 2017

Research Groups and Themes

BCS and TECS CDTs
Organic & Biological

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A 13C NMR Coldprobe to Underpin Chemistry Research.
Butts, C. P. (Principal Investigator)
28/02/14 → 29/11/17
Project: Research
3-month Core Capability for Chemistry Research
Crosby, J. (Principal Investigator)
1/01/13 → 1/04/13
Project: Research
Changing the Synthesis Landscape with Boron at the Helm: from Chiral Organometallics to Assembly Line Synthesis
Aggarwal, V. K. (Principal Investigator)
14/05/12 → 13/01/18
Project: Research

Lithiation and Borylation of Secondary O- and S- Substituted Hindered Benzoates
Songara, P. (Author), Russell, C. (Supervisor) & Aggarwal, V. (Supervisor), 11 May 2021
Student thesis: Doctoral Thesis › Doctor of Philosophy (PhD)

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title = "Asymmetric Synthesis of Tertiary Alcohols and Thiols via Nonstabilized Tertiary a-Oxy- and a-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.",

author = "Alex Pulis and Ana Varela and Cinzia Citti and Pradip Songara and Daniele Leonori and Varinder Aggarwal",

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

AU - Pulis, Alex

AU - Varela, Ana

AU - Citti, Cinzia

AU - Songara, Pradip

AU - Leonori, Daniele

AU - Aggarwal, Varinder

PY - 2017/8/28

Y1 - 2017/8/28

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.

U2 - 10.1002/anie.201706722

DO - 10.1002/anie.201706722

M3 - Article (Academic Journal)

C2 - 28783238

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 a-Oxy- and a-Thio-Substituted Organolithium Species

Abstract

Research Groups and Themes

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Projects

A 13C NMR Coldprobe to Underpin Chemistry Research.

3-month Core Capability for Chemistry Research

Changing the Synthesis Landscape with Boron at the Helm: from Chiral Organometallics to Assembly Line Synthesis

Student theses

Lithiation and Borylation of Secondary O- and S- Substituted Hindered Benzoates

Cite this