A Facile Synthesis of 1,1-Bis(silyl)ethenes

Abstract

Symmetrical 1,1-bis(silyl)ethenes have been easily prepared via ruthenium complex-catalyzed silylative coupling cyclization of 1,2-bis(dimethylvinylsiloxy)ethane to give 2,2,4,4-tetramethyl-3-methylene-1,5-dioxa-2,4-disilacycloheptane with excellent selectivity and good yield, followed by its reaction with Grignard reagents. The cyclic product can also be effectively transformed into cyclic carbosiloxane, 2,2,4,4,6,6,8,8-octamethyl-3,7-dimethylene-1,5-dioxa-2,4,6,8-tetrasilacyclooctane.

New cyclic and macrocyclic silaolefins via ring-closing metathesis of 1,1-bis(silyl)ethene-tethered dienes

“…The starting 1,1-bis(alkenyldimethylsilyl)ethenes were prepared according to our previously reported procedure [9]. In a preliminary experiment, we studied the ring-closing metathesis of 1,1-bis(dimethylvinylsilyl)ethene (1).…”

“…Although divinyl-substituted organosilicon compounds carrying electron-withdrawing substituents at silicon have been recently proved to be valuable substrates in the cross-metathesis with olefins [3], there is no data available on the reactivity of these compounds towards the RCM process. On the other hand, divinyl-substituted organosilicon compounds in the presence of ruthenium and rhodium complexes containing or generating M-H and M-Si (M = Ru, Rh) bonds, undergo competitive silylative coupling polycondensation [2,[4][5][6][7] and cyclization [2,[8][9][10][11][12][13] to give organosilicon oligomers or silicon-containing exo-methylenes, which cannot be prepared via ring-closing diene metathesis.…”

“…We have recently reported a new facile and efficient route for the synthesis of dialkenyl-and dialkenyloxysubstituted 1,1-bis(silyl)ethenes using cyclic silyl ether [9] or cyclic silyl amine [10] selectively obtained via ruthenium catalyzed deethenative silylative coupling cyclization of divinyl-substituted monomers, followed by their reaction with alkenyl Grignard reagents or alkenols (Scheme 1).…”

Acid-catalyzed reactions of (3-(naphthalen-2-yl)-2,2-bis(trimethylsilyl)oxiran. A new synthesis of functional-group-substituted vinylsilanes

“…Synthesis of (3-(naphthalen-2-yl)-2,2-bis(trimethylsilyl)) oxiran (2) A mixture of vinylsilane 1 (2.00 g, 6.71 mmol), MCPBA (75% w/w pure) and CH 2 Cl 2 (75 ml) was stirred at room temperature for 24 h. The mixture was washed with aq. NaHCO 3 (5 Â 40 ml), water (40 ml), brine (40 ml) and the organic layer was dried (MgSO 4 ).…”

“…2,2-Bis(trimethylsilyl)oxirans [1] are valuable reagents for the production of organosilicon compounds [2]. Ring-opening of epoxides with thiols is used widely in pharmaceutical and natural product chemistry [3].…”