18077-26-4Relevant articles and documents
Conventional lithium bases as unconventional sources of methyl anion: Facile Me-Si and Me-C bond cleavage in RLi, R2NLi, and BR4- by an electrophilic osmium dihydride
Yandulov, Dmitry V.,Huffman, John C.,Caulton, Kenneth G.
, p. 4030 - 4049 (2008/10/08)
cis,trans-Os(H)2(OTf)(NO)(PiPr3)2 (1-OTf) and several other precursors (1-X) to Os(H)2- (NO)(PiPr3)2+ (1+) react with (Me3Si)2NLi, (Me3Si)2CHLi, lithium 2,2,6,6-tetramethylpiperidide (TMPLi), Me3SiCH2Li, and B(CH2SiMe3)4- by a highly unusual, facile β-Me- transfer, the exclusive reaction pathway for the first two in nonpolar solvents. A series of lithium alkyls and alkylamides and organoborate reagents have been examined to reveal widespread occurrence of the direct β-R′- transfer (R′ = H, Me) to the Os electrophile, being completely selective for β-H- over β-Me-, with the sole (surprising) exception of NpLi. The β-R′ elimination was ruled out as the mechanism of the net β-R′- transfer for two representative RLi cases with R′ = H, Me, and a single-electron-transfer mechanism was shown to be inoperative for tetraalkylborates. The mechanistic studies also uncovered the important role of Li in RLi and R2NLi, which acts as a potent Lewis acid to abstract the halide/pseudohalide X from 1-X in generating the unsaturated Os species. The proposed intimate mechanism of Me-C and Me-Si bond cleavage is a direct SE2 substitution at carbon with inversion of the Me group, supported by DFT calculations. While the imines formed in the process of C-H and C-Me cleavage are lithiated by, and compete for the Os with, the original base, the unsaturated silicon species formed by Si-Me cleavage react with the remaining base by 1,2-addition of (N,C)-Li, forming intermediates that are also reactive by β-Me- transfer. A complex mixture of Os-free coproducts is obtained in both cases. The structural features of 1+ responsible for its unusual reactivity are discussed.
Rearrangement in borane adducts of trimethylsilylmethylenedimethylsulfurane
McMullen,Miller
, p. 2291 - 2295 (2008/10/08)
Boron halide, borane, and trimethylboron adducts of the silyl-substituted sulfonium ylide (CH3)3SiCHS(CH3)2 are readily formed. The borane and alkylboron adducts rearrange at low temperature with simultaneous loss of dimethyl sulfide to give sym-bis(trimethylsilylmethyl)diborane and 1-(trimethylsilylmethyl)ethyldimethylborane, respectively. These rearranged products were isolated and characterized. A trimethylamine adduct with the dialkyldiborane could be converted into the asymmetrical borane cations (CH3)3SiCH2BHN(CH3) 3py+ and (CH3)3SiCH2BHN(CH3) 3P(CH3)3+.
