Premium
Brook/Elimination/Aldol Reaction (BEAR) Sequence for the Direct Preparation of Fluorinated Aldols from β,β‐Difluoro‐α‐(trimethylsilyl)alcohols
Author(s) -
Decostanzi Mélanie,
Van Der Lee Arie,
Campagne JeanMarc,
Leclerc Eric
Publication year - 2015
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201500481
Subject(s) - aldol reaction , stereocenter , trimethylsilyl , chemistry , catalysis , sequence (biology) , fluoride , elimination reaction , base (topology) , stoichiometry , organic chemistry , enantioselective synthesis , inorganic chemistry , mathematical analysis , biochemistry , mathematics
A methodology allowing the preparation of aldols featuring a fluorinated stereogenic center is reported. The corresponding fluoroenolates are formed in situ from stable β,β‐difluoro‐α‐(trimethylsilyl)alcohols, through a base‐mediated process involving a Brook rearrangement followed by a fluoride elimination, and are directly added to aromatic aldehydes. Two different sets of conditions were disclosed. The first one involves the stoichiometric addition of potassium tert ‐butoxide ( t‐ BuOK) while the second is based on the use of a catalytic amount of an ammonium phenoxide. The latter opens the way for a catalytic and asymmetric version of this Brook/elimination/aldol reaction (BEAR) sequence.