Transition-Metal-Free Diboration of Non-Activated Olefins: A Reaction Mechanism Revisited.

Publication date: Available online 3 April 2018 Source:Computational and Theoretical Chemistry Author(s): Fredrik Haeffner Density functional theory (M06-2X/6-31+G∗) calculations were used to examine a mechanism (B2(1,1)) proposed by Fernández et al. (Angew. Chem., Int. Ed. 2011, 50, 7158) that tries to rationalize the high SYN-stereoselectivity observed in their discovered transition-metal-free diboration of non-activated olefins. The results show that B2(1,1) incorrectly predicts ANTI-addition of bulky diboron esters, however correctly predicts less bulky and catecholic diboron esters. Alternative mechanisms (B2 ’(1,1), B2(1,2), and B3), which help rationalize the stereochemistry of all studied diboron esters were examined. Graphical abstract

Source: Computational and Theoretical Chemistry - April 4, 2018 Category: Chemistry Source Type: research