Density functional computations of enantio selective alkynylation of aldehydes catalyzed by oxazaborolines. Part 1. Structures and properties of catalyst and intermediary states

作者：Li, M^*; He, RX

来源：Journal of Molecular Structure (Theochem), 2003, 629: 197-208.

DOI：10.1016/S0166-1280(03)00143-X

• enantioselective alkynylation
• mechanism
• chiral oxazaborolidine
• intermediary states
• density functional theory

In the present work, quantum chemical computations of the enantioselective alkynylation of aldehyde with alkynylborane catalyzed by chiral oxazaborolidine are performed by means of the density functional theory method. The structures of the catalyst and all the intermediary states for the alkynylation are optimized completely at the B3LYP/6-31G(d) level and their properties studied in detail. As illustrated, the alkynylation is exothermic and goes mainly through the formations of the catalyst-alkynylborane adduct, the catalyst-alkynylborane-aldehyde adduct, and the catalyst-alkoxyborane adduct. The chirality of the reduced products is of R type, which is in agreement with the experiment.

• 出版日期2003-7-4