TY - JOUR
T1 - Preparation of Functionalized Diaryl- and Diheteroaryllanthanum Reagents by Fast Halogen–Lanthanum Exchange
AU - Benischke, Andreas D.
AU - Anthore-Dalion, Lucile
AU - Berionni, Guillaume
AU - Knochel, Paul
N1 - Funding Information:
We thank the LMU Munich for financial support and the Humboldt foundation for a fellowship to L.A.-D. We also thank Albemarle and BASF for generous gifts of chemicals.
Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 2017/12/18
Y1 - 2017/12/18
N2 - Aryl and heteroaryl halides (X=Br, I) undergo a fast and convenient halogen–lanthanum exchange with nBu2LaMe, which leads to functionalized diaryl- and diheteroaryllanthanum derivatives. Subsequent trapping reactions with selected electrophiles, such as ketones, aldehydes, or amides, proceeded smoothly at −50 °C in THF, affording polyfunctionalized alcohols and carbonyl derivatives. Kinetic competition experiments revealed a similar reactivity trend as for Br/Mg exchange, but 106-times higher rates, making it comparable to Br/Li exchange.
AB - Aryl and heteroaryl halides (X=Br, I) undergo a fast and convenient halogen–lanthanum exchange with nBu2LaMe, which leads to functionalized diaryl- and diheteroaryllanthanum derivatives. Subsequent trapping reactions with selected electrophiles, such as ketones, aldehydes, or amides, proceeded smoothly at −50 °C in THF, affording polyfunctionalized alcohols and carbonyl derivatives. Kinetic competition experiments revealed a similar reactivity trend as for Br/Mg exchange, but 106-times higher rates, making it comparable to Br/Li exchange.
KW - 1,2-addition
KW - acylation
KW - halogen–lanthanum exchange
KW - kinetic studies
KW - lanthanum
UR - http://www.scopus.com/inward/record.url?scp=85034761689&partnerID=8YFLogxK
U2 - 10.1002/anie.201709553
DO - 10.1002/anie.201709553
M3 - Article
AN - SCOPUS:85034761689
SN - 1433-7851
VL - 56
SP - 16390
EP - 16394
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 51
ER -