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Palladium‐Catalyzed Chemoselective Allylic Substitution, Suzuki–Miyaura Cross‐Coupling, and Allene Formation of Bifunctional 2‐B(pin)‐Substituted Allylic Acetate Derivatives
Author(s) -
Kim ByeongSeon,
Hussain Mahmud M.,
Hussain Nusrah,
Walsh Patrick J.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402353
Subject(s) - chemoselectivity , allylic rearrangement , chemistry , catalysis , allene , palladium , bifunctional , combinatorial chemistry , organic chemistry , medicinal chemistry
A formidable challenge at the forefront of organic synthesis is the control of chemoselectivity to enable the selective formation of diverse structural motifs from a readily available substrate class. Presented herein is a detailed study of chemoselectivity with palladium‐based phosphane catalysts and readily available 2‐B(pin)‐substituted allylic acetates, benzoates, and carbonates. Depending on the choice of reagents, catalysts, and reaction conditions, 2‐B(pin)‐substituted allylic acetates and derivatives can be steered into one of three reaction manifolds: allylic substitution, Suzuki–Miyaura cross‐coupling, or elimination to form allenes, all with excellent chemoselectivity. Studies on the chemoselectivity of Pd catalysts in their reactivity with boron‐bearing allylic acetate derivatives led to the development of diverse and practical reactions with potential utility in synthetic organic chemistry.