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. 2019 Feb 4;58(6):1727-1731.
doi: 10.1002/anie.201812894. Epub 2019 Jan 15.

Stereoinversion of Unactivated Alcohols by Tethered Sulfonamides

Paul T Marcyk  1 , Latisha R Jefferies  1 , Deyaa I AbuSalim  1   2 , Maren Pink  1 , Mu-Hyun Baik  2   3 , Silas P Cook  1
Affiliations

Stereoinversion of Unactivated Alcohols by Tethered Sulfonamides

Paul T Marcyk et al. Angew Chem Int Ed Engl. .

Abstract

The direct, catalytic substitution of unactivated alcohols remains an undeveloped area of organic synthesis. Moreover, catalytic activation of this difficult electrophile with predictable stereo-outcomes presents an even more formidable challenge. Described herein is a simple iron-based catalyst system which provides the mild, direct conversion of secondary and tertiary alcohols to sulfonamides. Starting from enantioenriched alcohols, the intramolecular variant proceeds with stereoinversion to produce enantioenriched 2- and 2,2-subsituted pyrrolidines and indolines, without prior derivatization of the alcohol or solvolytic conditions.

Keywords: alcohol substitution; asymmetric synthesis; indoline; iron; sulfonamides.

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Conflict of interest statement

Conflict of interest

The authors declare no conflict of interest.

Figures

Scheme 1.
Scheme 1.
An ion-pair approach to enantioselective substitution.
Scheme 2.
Scheme 2.
Stereochemical model and absolute configuration for the intramolecular substitution of (a) secondary alcohols (b) tertiary alcohols. (c) Absolute configuration determination for indoline product 6a by an asymmetric benzylation of d-alanine derivative 8.
Scheme 3.
Scheme 3.
Computed free-energy diagram for the intramolecular substitution of 3a.
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