Search

Herein, we report the synthesis and catalytic application of a new N,N′-dineopentyl-1,2-phenylenediamine-based bismuthenium cation (3). 3 has been synthesized via the treatment of chlorobismuthane LBiCl [L = 1,2-C6H4{N(CH2tBu)}2] (2) with AgSbF6, and was further used as a robust catalyst for the cyanosilylation of ketones under mild reaction conditions. Experimental studies and DFT calculations were performed to understand the mechanistic pathway. [ABSTRACT FROM AUTHOR]

The synthesis of novel stibenium cations and their catalytic application in cyanosilylation of carbonyl compounds have been described. Treatment of chlorostibine L1SbCl [L1 = 1,2-C6H4{N(CH2tBu)}2] (2) with 1 equiv. of AgOTf and AgSbF6 resulted in the formation of donor free L1SbOTf (3) and [L1Sb]+[SbF6]− (4), respectively. Among these three compounds, 4 exhibits excellent catalytic activity towards the cyanosilylation of aldehydes and ketones. [ABSTRACT FROM AUTHOR]

Herein, we have undertaken the synthesis and investigated the reactivity of a 6-membered saturated NHC borane adduct (1). Direct electrophilic halogenation of 1 with a stoichiometric amount of I2 led to NHC boryl iodides, 6-SIDipp·BH2I (2) and 6-SIDipp·BHI2 (3), which were further reacted with various nucleophiles to give novel 6-SIDipp based mono and disubstituted boranes with OTf (4 and 6) or ONO2 (5 and 7) functional groups. The addition of Br2/H2O to 1 smoothly results in a dihydroxyborenium cation (8). [ABSTRACT FROM AUTHOR]