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Catalytic Reductive Pinacol‐Type Rearrangement of Unactivated 1,2‐Diols through a Concerted, Stereoinvertive Mechanism
Author(s) -
Drosos Nikolaos,
Cheng GuiJuan,
Ozkal Erhan,
Cacherat Bastien,
Thiel Walter,
Morandi Bill
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201704936
Subject(s) - pinacol , deoxygenation , catalysis , chemistry , reaction mechanism , silanes , reductive elimination , combinatorial chemistry , organic chemistry , photochemistry , silane
A catalytic pinacol‐type reductive rearrangement reaction of internal 1,2‐diols is reported herein. Several scaffolds not usually amenable to pinacol‐type reactions, such as aliphatic secondary–secondary diols, undergo the transformation well without the need for prefunctionalization. The reaction uses a simple boron catalyst and two silanes and proceeds through a concerted, stereoinvertive mechanism that enables the preparation of highly enantiomerically enriched products. Computational studies have been used to rationalize the preference for migration over direct deoxygenation.