18586-58-8Relevant academic research and scientific papers
Design, synthesis, and electrochemical behavior of new electronic systems involving σ,σ- and σ,π-interaction
Nishiwaki, Keiji,Yoshida, Jun-Ichi
, p. 787 - 788 (1996)
1,2-Bis(trimethylsilyl)-1,2-diphenylethane and its homologues were synthesized and the studies on their electrochemical behavior revealed that there is definite interaction between the σ,π-interaction system (the C-Si bonds and the benzene rings) and the σ,σ-interaction system (the neighboring C-Si bonds) which causes significant decrease of the oxidation potentials.
Copper-Catalyzed Twofold Silylmetalation of Alkynes
Shimokawa, Jun,Yamagishi, Hiroki,Yorimitsu, Hideki
supporting information, p. 1551 - 1554 (2019/08/07)
The first twofold silylmetalation across a C≡C triple bond was achieved. In the presence of a catalytic amount of copper cyanide, diarylacetylenes were converted into 1,2-dimetalated 1,2-disilyl-1,2-diarylethanes on treatment with silylpotassium species generated in situ from disilane and t -BuOK. The dimetalated species were subsequently protonated to yield a series of 1,2-disilyl-1,2-diarylethanes.
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.
SET and exciplex pathways in the photochemical reactions between aromatic ketones and benzylsilane and stannane derivatives
Cermenati, Laura,Freccero, Mauro,Venturello, Paolo,Albini, Angelo
, p. 7869 - 7876 (2007/10/02)
The photochemical reaction of α,α,α-trifluoroacetophenone (TFA), benzophenone, and p-cyanoacetophenone with benzyltrimethylsilane in MeCN involves hydrogen transfer from the benzylic position. Desilylation occurs as a minor process only in the case of TFA (but it increases greatly in the presence of MeOH or LiClCO4). The final products result from the statistical recombination of the benzyl and ketyl radicals. Further cases of intramolecular selectivity studied are p-methylbenzyl- and p-methoxybenzyltrimethylsilane (the latter substrate undergoes mainly C-Si bond cleavage in the reaction with TFA) as well as benzyltributylstannane (only destannylation observed with all ketones). Product studies are complemented by the determination of relevant kinetic parameters through steadystate and flash-photolysis experiments. The results are explained in terms of hydrogen transfer proceeding from an exciplex and desilylation from the solvent separated radial ion pair. The latter species predominates when ΔGet -1.
Unprecedented McMurry Reactions with Acylsilanes: Enedisilane Formation versus Brook Rearrangement
Fuerstner, Alois,Seidel, Guenter,Gabor, Barbara,Kopiske, Carsten,Krueger, Carl,Mynott, Richard
, p. 8875 - 8888 (2007/10/03)
The first inter- and intramolecular McMurry reactions of aroyltrimethylsilanes to substituted 1,2-bis(trimethylsilyl)ethene derivatives 2a-c and 7 are described.A low-valent titanium reagent prepared by the reduction of TiCl3 with Na on inorganic supports (Al2O3, NaCl, TiO2) turned out to be best suited.Depending on the reaction conditions and on the particular substitution patterns of substrates, Brook rearrangements of the intermediate 1,2-disilylated titanium-1,2-diolates leading to the formation of C,O-disilyl-enol ethers may compete with the McMurry deoxygenation pathway.
Carbanion Rearrangements of ω-Phenyl-ω-(trimethylsilyl)alkyllithium Compounds: Intramolecular Reactions of Benzyltrimethylsilanes with a Carbon-Lithium Bond
Maercker, Adalbert,Stoetzel, Reinhard
, p. 1695 - 1706 (2007/10/02)
ω-Phenyl-ω-(trimethylsilyl)alkyllithium compounds show four out of five theoretically conceivable possibilities for intramolecular stabilization depending on the solvent and on the chain length n.While transmetalation of a methyl group at the silicon atom by a 1,(n+2) proton transfer is observed in any case, the intramolecular 1,n shift of the benzylic proton does only take place with n >/= 4.The main reaction, however for n = 3 and 4 only, is represented by the 1,n trimethylsilyl shift via a cyclic ate complex as an intermediate which partly splits off methyllithium yielding the corresponding silacycloalkane derivatives.In going from diethyl ether to THF as the solvent, the silyl shifts are more accelerated than the proton shifts.In no case, however, a Grovenstein-Zimmermann rearrangement involving phenyl migration took place.Degenerate silyl shifts starting from α-deuterated ω-(trimethylsilyl)alkyllithium compounds could not be detected either.Only by introduction of a second trimethylsilyl group into the 3 position a 1,3-(C -> C)-trimethylsilyl shift is initiated again.
1,n-TRIORGANOSILYL MIGRATIONS IN THE REARRANGEMENTS OF SILYL-SUBSTITUTED ORGANOLITHIUM COMPOUNDS
Eisch, John J.,Tsai, Miin-Rong
, p. 5 - 24 (2007/10/02)
Under the agency of the potent lithiating agent, n-butyllithium in TMEDA, an array of organosilanes was found to undergo 1,n-silyl rearangements via carbanionic intermediates.Unambiguous 1,2-, 1,3- and 1,4-silyl shifts were unconvered in 1-trimethylsilyl-
