1719-04-6Relevant articles and documents
DMF-activated chlorosilane chemistry: Molybdenum-catalyzed reactions of R3SiH, DMF and R′3SiCl to initially form R′3SiOSiR′3 and R3SiCl
Gonzalez, Paulina E.,Sharma, Hemant K.,Pannell, Keith H.
, p. 376 - 381 (2017/06/30)
The room temperature reactions between R3SiH (R3?=?Et3, PhMe2, Ph2Me) and R′3SiCl (R′3?=?Me3, PhMe2, Ph2Me), with an excess of dimethylformamide (DMF) in the presence of (Me3N)Mo(CO)5 as a catalyst, result in the initial formation of R3SiCl, R′3SiOSiR′3 and Me3N as detected by 29Si, 13C, 1H NMR spectroscopy and GC/MS. As the reaction proceeds, the more so if the reaction temperature is raised, mixed disiloxanes R3SiOSiR′3 and ultimately lesser amounts of R3SiOSiR3 may be detected. A mechanism involving the activation of chlorosilanes by the nucleophilic DMF is proposed to produce transient imminium siloxy ion pairs, [Me2N[dbnd]CHCl]+[R′3SiO]? ? [Me2N[dbnd]CH(OSiR′3)]+Cl? which react with R3SiH to form Me2NCH2OSiR′3 and R3SiCl. A secondary reaction of Me2NCH2OSiR′3 with R′3SiCl produces the symmetrical disiloxane R′3SiOSiR′3 and ClCH2NMe2. The final stage of the reaction is the reduction of ClCH2NMe2 by R3SiH, a reaction which is reported for the first time. The newly created chlorosilane R3SiCl can become involved in the initial DMF activation chemistry thereby forming the other disiloxanes observed as the reaction proceeds.
Pd/C-catalyzed cross-coupling reaction of benzyloxysilanes with halosilanes for selective synthesis of unsymmetrical siloxanes
Igarashi, Masayasu,Kubo, Keiko,Matsumoto, Tomohiro,Sato, Kazuhiko,Ando, Wataru,Shimada, Shigeru
, p. 19099 - 19102 (2014/05/20)
A new protocol for the nonhydrolytic synthesis of unsymmetrical siloxanes has been developed. The cross-coupling reaction of benzyloxysilanes with halosilanes catalyzed by Pd/C afforded various unsymmetrical siloxanes with co-production of benzyl halides. the Partner Organisations 2014.
OXIDATION OF ORGANOPOLYSILANES WITH ?- AND n-DONOR SUBSTITUENTS WITH PEROXYBENZOIC ACID
Razuvaev, G. A.,Brevnova, T. N.,Semenov, V. V.,Kornev, A. N.,Lopatin, M. A.,Egorochkin, A. N.
, p. 323 - 330 (2007/10/02)
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