Unsymmetrical 1

Identificador:  imarina:3665101

Handle: https://hdl.handle.net/20.500.11797/imarina3665101

Autors:  Cuenca, Ana B; Cid, Jessica; Garcia-Lopez, Diego; Carbo, Jorge J; Fernandez, Elena

Resum:
We have experimentally proved the unsymmetrical 1,1-diboration of diazo compounds, formed in situ from aldehydes and cyclic and non-cyclic ketones, in the absence of any transition metal complex. The heterolytic cleavage of the mixed diboron reagent, Bpin-Bdan, and the formation of two geminal C-Bpin and C-Bdan bonds has been rationalised based on DFT calculations to occur via a concerted-asynchronous mechanism. Diastereoselection is attained on substituted cyclohexanones and DFT studies provide understanding on the origin of the selectivity. The alkoxide-assisted selective deborylation of Bpin from the multisubstituted sp3-carbon and generation of a Bdan stabilized carbanion, easily conducts a selective protodeboronation sequence