TY - JOUR
T1 - Enantio- and diastereodivergent dual catalysis
T2 - α-Allylation of branched aldehydes
AU - Krautwald, Simon
AU - Sarlah, David
AU - Schafroth, Michael A.
AU - Carreira, Erick M.
N1 - Copyright:
Copyright 2015 Elsevier B.V., All rights reserved.
PY - 2013/5/31
Y1 - 2013/5/31
N2 - An important challenge in asymmetric synthesis is the development of fully stereodivergent strategies to access the full complement of stereoisomers of products bearing multiple stereocenters. In the ideal case, where four products are possible, applying distinct catalysts to the same set of starting materials under identical conditions would in a single step afford any given stereoisomer. Herein, we describe the realization of this concept in a fully stereodivergent dual-catalytic synthesis of γ,δ-unsaturated aldehydes bearing vicinal quaternary/tertiary stereogenic centers. The reaction is enabled by chiral iridium and amine catalysts, which activate the allylic alcohol and aldehyde substrates, respectively. Each catalyst exerts high local stereocontrol irrespective of the other's inherent preference.
AB - An important challenge in asymmetric synthesis is the development of fully stereodivergent strategies to access the full complement of stereoisomers of products bearing multiple stereocenters. In the ideal case, where four products are possible, applying distinct catalysts to the same set of starting materials under identical conditions would in a single step afford any given stereoisomer. Herein, we describe the realization of this concept in a fully stereodivergent dual-catalytic synthesis of γ,δ-unsaturated aldehydes bearing vicinal quaternary/tertiary stereogenic centers. The reaction is enabled by chiral iridium and amine catalysts, which activate the allylic alcohol and aldehyde substrates, respectively. Each catalyst exerts high local stereocontrol irrespective of the other's inherent preference.
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U2 - 10.1126/science.1237068
DO - 10.1126/science.1237068
M3 - Article
C2 - 23723229
AN - SCOPUS:84878349078
SN - 0036-8075
VL - 340
SP - 1065
EP - 1068
JO - Science
JF - Science
IS - 6136
ER -