A Theoretical Study of the Reaction of Alkynylboranes with Butadiene: Competition between Cycloaddition and Alkynylboration

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Abstract

The reactions of alkynyldihaloboranes and alkynyldialkylboranes with butadiene have been explored by using DFT methods at the B3LYP level with the 6-31G basis set. Transition structures for the concerted [4+2] cycloaddition have been found for the alkynylborane derivatives. Along with these, another reactive pathway has been found for the cycloaddition process with transition structures of high [4+3] character. The transition structures for the 1,4-alkynylboration processes have also been found. The geometries computed for the cycloaddition transition structure with high [4+3] character and the 1,4-alkynylboration transition structures are surprisingly similar though leading to different products. IRC calculations suggest that the [4+3] cycloaddition and alkynylboration pathways are associated by a zwitterionic structure.

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