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These calculations show that the isomer 1,2\u2010B<jats:sub>2<\/jats:sub>cat<jats:sub>2<\/jats:sub> in\u2005situ generated from 1,1\u2010B<jats:sub>2<\/jats:sub>cat<jats:sub>2<\/jats:sub> induced by DMA is the reactive boron intermediate for the reactions. The addition of the B\u2212B bond of 1,2\u2010B<jats:sub>2<\/jats:sub>cat<jats:sub>2<\/jats:sub> to the C=O bond of acetone or benzaldehyde via a concerted [2\u03c3+2\u03c0]\u2010cycloaddition\u2010like transition state is the rate\u2010limiting step for both the triboration reaction of acetone and the monoboration reaction of benzaldehyde. DMA not only acts as the solvent but also promotes the structural isomerization of B<jats:sub>2<\/jats:sub>cat<jats:sub>2<\/jats:sub>, the deoxygenation of acetone to form the vinyl boronate intermediate and subsequent diboration of vinyl boronate with 1,2\u2010B<jats:sub>2<\/jats:sub>cat<jats:sub>2<\/jats:sub>, as well as the protodeboronation of the gem\u2010diboronate intermediate in the deoxygenative borylation of benzaldehyde. The presented computational results can explain the observed experimental facts and provide insight into the roles of the isomeric 1,2\u2010B<jats:sub>2<\/jats:sub>cat<jats:sub>2<\/jats:sub> and the solvent DMA in related reactions.<\/jats:p>","DOI":"10.1002\/chem.202203526","type":"journal-article","created":{"date-parts":[[2022,12,22]],"date-time":"2022-12-22T10:24:20Z","timestamp":1671704660000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Mechanistic Insights into the Metal\u2010Free Deoxygenative Borylation of Ketones and Aldehydes with Bis(catecholato)diborane"],"prefix":"10.1002","volume":"29","author":[{"given":"Wentian","family":"Zou","sequence":"first","affiliation":[{"name":"Key Laboratory of Mesoscopic Chemistry of Ministry of Education Institute of Theoretical and Computational Chemistry School of Chemistry and Chemical Engineering Nanjing University  Nanjing 210023 P. R. 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