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Pd‐Catalyzed Stereodivergent Allylic Amination of α‐Tertiary Allylic Alcohols towards α,β‐Unsaturated γ‐Amino Acids
Author(s) -
Xie Jianing,
Qiao Chang,
Martínez Belmonte Marta,
EscuderoAdán Eduardo C.,
Kleij Arjan W.
Publication year - 2019
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201900433
Subject(s) - allylic rearrangement , amination , chemistry , stereoselectivity , catalysis , ligand (biochemistry) , amine gas treating , organic chemistry , medicinal chemistry , palladium , combinatorial chemistry , biochemistry , receptor
Tertiary allylic alcohols were conveniently converted into either ( Z )‐ or ( E )‐configured α,β‐unsaturated γ‐amino acids by treatment with secondary amines under Pd catalysis at ambient conditions. The key to control the stereochemical course of these formal allylic aminations was the presence of a suitable diphosphine ligand, with dppp [1,3‐bis(diphenylphosphino)propane, L12 ] providing high yields and selectivities for the ( Z ) isomers, whereas the bis[(2‐diphenylphosphino)phenyl]ether (DPEPhos) derivative L1′ allowed for selective formation of the corresponding ( E ) isomeric products. This ligand‐controlled, stereodivergent protocol thus shows promise for the stereoselective preparation of allylic amine products from a common substrate precursor.