Diastereospecific Coupling of Imines by Low‐Valent Titanium: An Experimental and Computational Study

Abstract

AbstractThe reaction of phenylsilane (PhSiH3) and titanium(IV) isopropoxide [Ti(OiPr)4] generates low‐valent titanium alkoxides that reduce and reductively couple imines. The C–C coupling reaction is diastereospecific, with exclusive formation of the (±)‐isomer. The yield is dependent on the concentration of titanium(IV) isopropoxide used. Using imines with varying electronic demand revealed that the coupling is most efficient for unsubstituted imines. The involvement of a trimeric titanium biradical species is invoked to explain the observed concentration dependence and diastereospecificity in the reaction. Multilayer ONIOM (“our own n‐layered integrated molecular orbital and molecular mechanics”) calculations were carried out on the plausible intermediates involved by using the Guassian 09 suite of programs. Formation of the trimeric biradical species leading to the formation of the (±)‐isomer is more favored than formation of the trimeric biradical species, which leads to the meso‐isomer. Similar calculations with dimeric intermediates do not predict the (±)‐selectivity. Mass spectral analysis of the reaction mixture indicates the presence of a trimeric titanium alkoxide species.