Alkynes 9-borabicyclo nonane dimer

Wang, K. K., Scouten, C. G., Brown, H. C. Hydroboration kinetics. 3. Kinetics and mechanism of the hydroboration of alkynes with 9-borabicyclo[3.3.1]nonane dimer. Effect of structure on the reactivity of representative alkynes. J. Am. Chem. Soc. 1982,104, 531-536. 

TMS-alkynes are oxidized at the terminal carbon to carboxylic acids by hydroboration/oxidation (dicyclohexylborane/NaOH, H2O2). This does not work with TIPS-alkynes. Instead, TIPS-alkynes are cleanly monohydroborated at the internal carbon by 9-borabicyclo[3.3.1]nonane dimer to give (Z)- -borylvinyl-silanes. These can be oxidized in high yields to a-silyl ketones, or cross coupled with a bromide R Br (R = aryl, benzyl, dimethyl-vinyl) in the presence of NaOH and tetrakis(triphenylphos-phine)palladium(0) to give /3,/3-disubstituted vinylsilanes (Suzuki reaction eq 14). The same nucleophilic substituted vinylsilane can be added to an aromatic aldehyde to provide access to ( )-3-silyl allyl alcohols. ... 

Brown and co-workers have continued their extensive studies of the mechanisms of hydroboration. Some of this work has recently been reviewed. Kinetic studies have been reported of the reaction of 9-borabicyclo[3.3.1]nonane dimer (3) with alkenes, alkynes, aldehydes, and ketones, in various solvents and with various Lewis bases and Br0nsted acids. Earlier studies suggested that the reaction of (3) with alkenes in a variety of solvents proceeded via the initial dissociation as in equation (4) to the monomer (4) followed by the hydro-... 

Borabicyclo[3.3.1]nonane (9-BBN) has found use in the selective hydro-boration of alkenes in the presence of other reducible functional groups and its reaction with alkynylstannates has been studied. o-Stannyl- and a-silyl-substituted crotyl-9-BBN show promise as reagents for the stereo-regulated synthesis of acyclic systems. A series of papers covers the question of olefin-alkyl exchange in. 5-alkyl-9-BBN s, " the kinetics of reduction of substituted benzaldehydes with 9-BBN, and the kinetics and mechanism of hydroboration of alkynes with 9-BBN dimers. Selective dehalogenation of tertiary alkyl, benzyl, and allyl halides in the presence of secondary or primary alkyl or aryl halides is possible with (165). The... 

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See also in sourсe #XX -- [ ]

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