86393-01-3Relevant academic research and scientific papers
Synthesis of Enantioenriched Allylic Silanes via Nickel-Catalyzed Reductive Cross-Coupling
Hofstra, Julie L.,Cherney, Alan H.,Ordner, Ciara M.,Reisman, Sarah E.
supporting information, p. 139 - 142 (2018/01/17)
An asymmetric Ni-catalyzed reductive cross-coupling has been developed to prepare enantioenriched allylic silanes. This enantioselective reductive alkenylation proceeds under mild conditions and exhibits good functional group tolerance. The chiral allylic silanes prepared here undergo a variety of stereospecific transformations, including intramolecular Hosomi-Sakurai reactions, to set vicinal stereogenic centers with excellent transfer of chirality.
Activation Parameters for the Reaction of Phenylchloro Carbene with Pyridine, Tri-n-butyltin Hydride, and Triethylsilane; Evidence Against the Need to Invoke Reversibly Formed Complexes in the Reaction of This Carbene with Olefins
Jackson, James E.,Soundararajan, N.,Platz, Matthew S.,Doyle, Michael P.,Liu, Michael T. H.
, p. 1335 - 1338 (2007/10/02)
The activation energies for reaction of phenylchloro carbene with pyridine, tri-n-butyl-tin hydride and triethylsilane are reported.The data argues against reversibly formed complexes in the reaction of this carbene with olefins.
REACTIVITY AND SELECTIVITY IN INTERMOLECULAR INSERTION REACTIONS OF CHLOROPHENYLCARBENE
Doyle, Michael P.,Taunton, Jack,Oon, Su-Min,Liu, Michael T. H.,Soundararajan, N.,et. al.
, p. 5863 - 5866 (2007/10/02)
Reactivities for intermolecular C-H/Si-H/Sn-H insertion reactions of chlorophenylcarbene follow the order tri-n-butyltin hydride>>diphenylsilane>triethylsilane>>cumene>ethylbenzene>>toluene, and these reactions are competitive with addition to the double bond of α,β-unsaturated esters.
A PHENYLCARBENE TRANSFER SYSTEM
Cunico, Robert F.,Chu, Kuang S.
, p. 271 - 278 (2007/10/02)
Treatment of (α,α-dichlorobenzyl)trimethylsilane with potassium fluoride/18-crown-6 ether/diglyme transfers phenylchlorocarbene to a number of carbenophiles at room temperature.
Reduction of Halosilanes by Organotin Hydrides
Wilt, James W.,Belmonte, Frank G.,Zieske, Paul A.
, p. 5665 - 5675 (2007/10/02)
A study of the reduction of halosilanes with organotin hydrides is described.The free radical chain mechanism indicated by the results obtained parallels that known for the comparable reduction of haloalkanes, but the reactivity of α-haloalkanes is considerable enhanced.Mechanistic studies suggest that the polar nature of the halogen abstraction step in the radical chain sequence, which places incremental negative charge adjacent to silicon, is the principal reason for this enhanced reactivity.Structure-reactivity studies indicat the gem-dimethylsilyl function to be an electronic transmitter.The ρ values for reduction of aryldimethyl(chloromethyl)silanes and substituted benzyl chlorides by tri-n-butyltin hydride are essentially identical (+0.45).Reduction of (chloromethyl)trimethylsiulane with aryldimethyltin hydrides, conversely, yielded a ρ value of -1.61.The reduction produced racemic product from an optically active α-chlorosilane, the synthesis of which appears to the first reported.Other syntheses of variuos halosilanes of interest are also described.The title reduction is specific for carbon-halogen bonds.Silicon-halogen bonds are not affected, a distinction that should make the reduction synthetically useful.Because the increased reactivity of α-halosilanes in the reduction has thus been ascribed to a kinetic polar effect in a critical step of the mechanism, no compelling argument for special thermodynamic stability in α-silyl radicals themselves can be made.
