Premium
Gold‐Catalyzed Iminations of Terminal Propargyl Alcohols with Anthranils with Atypical Chemoselectivity for C(1)‐Additions and 1,2‐Carbon Migration
Author(s) -
Skaria Manisha,
More Sayaji Arjun,
Kuo TungChun,
Cheng MuJeng,
Liu RaiShung
Publication year - 2020
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.201905283
Subject(s) - chemoselectivity , propargyl , carbene , chemistry , substituent , medicinal chemistry , catalysis , regioselectivity , nucleophile , alkyl , organic chemistry
This work reports gold‐catalyzed iminations of terminal propargyl alcohols with anthranils or isoxazoles to yield E ‐configured α‐amino‐2‐en‐1‐ones and ‐1‐als with complete chemoselectivity. These catalytic iminations occur exclusively with C(1)‐nucleophilic additions on terminal alkynes, in contrast to a typical C(2)‐route. For 3,3‐dialkylprop‐1‐yn‐3‐ols, a methyl substituent is superior to long alkyl chains as the 1,2‐migration groups toward α‐imino gold carbenes. For secondary prop‐1‐yn‐3‐ols, phenyl, vinyl, and cyclopropyl substituents are better than hydrogen as the migrating groups, obviating typical gold carbene reactions. DFT calculations have been performed to rationalize the observed C(1)‐regioselectivity and the preferable cyclopropyl migration based on gold carbene pathways.