Concerning the potential reversibility of carbometalation in alkoxide-directed Ti(Oi-Pr)4-mediated reductive cross-coupling of homoallylic alcohols with aromatic imines.
In an attempt to understand the nature of selectivity in Ti-mediated reductive cross-coupling between homoallylic alcohols and imines, we investigated whether thermodynamic equilibration of the presumed organometallic intermediate plays a role in selectivity. No evidence could be found for olefin exchange in preformed azatitanacyclopentanes--an observation that is consistent with a model based on kinetically controlled selective carbometalation.
Takahashi
Masayuki
M
Department of Chemistry, The Scripps Research Institute, Scripps-Florida, Jupiter, FL, USA. micalizio@scripps.edu.
Micalizio
Glenn C
GC
D007097:Imines / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D020005:Propanols / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
D007097:Imines; D009942:Organometallic Compounds; D020005:Propanols; C006463:allyl alcohol; C102815:titanium isopropoxide