Premium
Cyclization of Trichloroacetimidates by Olefin Aminopalladation β‐Heteroatom Elimination
Author(s) -
Maleckis Ansis,
Jaunzeme Ieva,
Jirgensons Aigars
Publication year - 2009
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200900917
Subject(s) - chemistry , heteroatom , allylic rearrangement , chirality (physics) , olefin fiber , stereoselectivity , stereochemistry , medicinal chemistry , catalysis , organic chemistry , ring (chemistry) , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model , quark
The cyclization of δ‐acetoxy‐ O ‐allyl‐ and ϵ‐acetoxy‐ O ‐homoallyl‐trichloroacetimidates to 4‐vinyloxazolines and a 4‐vinyldihydrooxazine has been efficiently achieved by olefin aminopalladation–β‐heteroatom elimination. ( Z )‐Allylic imidates bearing a secondary δ‐acetoxy group underwent Pd II ‐catalysed cyclization to give the E isomers of 4‐vinyloxazolines selectively and gave no Overman rearrangement products. Using a chiral substrate, it has been demonstrated that cyclization to 4‐vinyloxazolines occurs with high chirality transfer. Stereoselective E isomer formation and chirality transfer provided a basis from which to discuss the possible reaction mechanism. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)