80279-02-3Relevant academic research and scientific papers
Copper-Catalyzed Cross-Coupling of Vinyliodonium Salts and Zinc-Based Silicon Nucleophiles
Zhang, Liangliang,Oestreich, Martin
supporting information, p. 8061 - 8063 (2019/01/14)
A silylation of vinyliodonium salts using zinc-based silicon reagents as nucleophiles is reported. This cross-coupling is catalyzed by copper, and vinylsilanes are obtained in high yield likely following a Cu(I)/Cu(III) reaction mechanism. The procedure i
Cationic rearrangements controlled by the presence of a silyl group
Chénedé, Alain,Fleming, Ian,Salmon, Roger,West, Mark C.
, p. 84 - 93 (2007/10/03)
1,1-Disilylcarbinols having two alkyl groups on the adjacent carbon atom react with thionyl chloride in sulfur dioxide to give the product in which one of the alkyl groups has migrated towards the two silyl groups, and one of the silyl groups has been removed from the resultant cation. The reaction is seen in ring-expansion, as in the conversion of cyclohexylbis[dimethyl(phenyl)silyl]carbinol (7) into 1-dimethyl(phenyl) silylcycloheptene (11), and in open chains, as in the conversion of 1,1-bis[dimethyl(phenyl)silyl]-2-methylpropanol (26) into (E)- and (Z)-2-dimethyl(phenyl)silylbut-2-ene (27). Phenyldimethylsilyllithium reacts with pinacolone to give the α-silyl carbinol (44), which rearranges in the same way to give 2,3-dimethylbut-2-ene (46), effectively achieving a pinacolone-to-pinacol rearrangement.
THE ASYMMETRIC HYDROBORATION OF SIMPLE ALKENYLSILANES: CHIRAL α-SILYLALKYL-BORANES AND ALCOHOLS
Soderquist, John A.,Lee, Shwn-Ji Hwang
, p. 4033 - 4042 (2007/10/02)
The detailed study of the asymmetric hydroboration of various vinylsilanes with monoisopinocampheylborane (IPCBH2) is presented.In all cases, β substitution on the vinylsilane gives monomeric dialkylborane adducts with the boryl group α to the silicon.These studies shown that the larger the groups on silicon are, the more positive the influence on the enatioselectivity of the process.Moderate asymmetric induction (24-40percent) is observed only for vinyl silanes wich contain a substituent trans to the silicon.A model for the asymmetric hydroboration of alkenes with this reagent is proposed.The complete charactarization of the borane intermediates was achieved employing NMR (11B, 13C, 1H, 29Si).
ORGANIC SYNTHESIS WITH REAGENTS DERIVED FROM 3R3SiMgMe AND MnCl2
Fugami, Keigo,Hibino, Jun-ichi,Nakatsukasa, Shigeki,Matsubara, Seijiro,Oshima, Koichiro,et al.
, p. 4277 - 4292 (2007/10/02)
Synthetically useful reactions mediated by reagents derived from 3 equiv. of R3SiMgMe and MnCl2 are disclosed. (1) The manganese species reacted with terminal acetylenes to give 1,2-disilylated 1-alkenes.Mono- and bis(trimethylsilyl)acetylenes gave tri- a
NEW SYNTHESES OF VINYLSILANES AND ALLYLSILANES BY CROSS-COUPLING OF (R3Si)3MnMgMe WITH ALKENYL AND ALLYLIC COMPOUNDS
Fugami, Keigo,Oshima, Koichiro,Utimoto, Kiitiro,Nozaki, Hitosi
, p. 2161 - 2164 (2007/10/02)
The reaction of alkenyl halides, alkenyl sulfides, and enol phosphates with (R3Si)3MnMgMe provides vinylsilanes in good yields.The method is also applicable to the allylsilane synthesis from allylic sulfides and ethers.
The Silylcupration of Acetylenes: a Synthesis of Vinylsilanes
Fleming, Ian,Newton, Trevor W.,Roessler, Felix
, p. 2527 - 2532 (2007/10/02)
Bis(dimethylphenylsilyl)copper-lithium (1) reacts with hex-1-yne, propyne, acetylene itself, phenylacetylene, and hex-3-yne to give the products of syn addition of the dimethylphenylsilyl group and the copper.The resultant vinylcopper reagents react with a variety of electrophiles, such as the proton, iodine, acyl and alkyl halides, enones, and epoxides, to give vinylsilanes.With the terminal alkynes, the silyl group becomes attached with a high level of regioselectivity to the terminal carbon atom, with the result that the final products are 2,2-disubstituted vinylsilanes.
