Open AccessGeneration of Masked TiII Intermediates from TiIV Amides via β-H Abstraction or Alkyne Deprotonation: An Example of Ti-Catalyzed Nitrene-Coupled Transfer Hydrogenation
Author(s) -
Adam J. Pearce,
Yukun Cheng,
Rachel J Dunscomb,
Ian A. Tonks
Publication year - 2020
Publication title -
organometallics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.231
H-Index - 172
eISSN - 1520-6041
pISSN - 0276-7333
DOI - 10.1021/acs.organomet.0c00577
Subject(s) - chemistry , nitrene , alkyne , deprotonation , catalysis , amide , protonolysis , photochemistry , transfer hydrogenation , hydrogen atom abstraction , medicinal chemistry , hydrogen , organic chemistry , ion , ruthenium
Simple Ti amide complexes are shown to act as sources for masked Ti II intermediates via several pathways, as demonstrated through the investigation of a unique Ti-catalyzed nitrene-coupled transfer hydrogenation of 3-hexyne. This reaction proceeds through reduction of azobenzene by a masked Ti II catalyst, wherein both amines and 3-hexyne can serve as the hydrogen source/reductant for Ti by forming putative titanaziridines via β -H abstraction or putative titanacyclopentynes via protonolysis, respectively.