Chemische Berichte p. 1709 - 1714 (1997)
Update date:2022-08-11
Topics:
Gross, Thoralf
Kempe, Rhett
Oehme, Hartmut
Tris(trimethylsilyl)silyllithium (1) reacts with methyl formate in diethyl ether (molar ratio 2:1) to give l,2-di(hypersilyl)ethylene 13. The formation of 13 proceeds through the intermediates formyl tris(trimethylsilyl)silane (4) and lithium bis[tris(trimethylsilyl)silyl]methoxide (5). In diethyl ether, the alkoxide 5 spontaneously eliminates lithium trimethylsilanolate thereby generating l,l-bis(trimethylsilyl)-2-[tris{trimethylsilyl)silyl]silene (9), which undergoes a formal [2+2] cycloaddition with the carbonyl compound 4 to afford 13. This was verified by crossover experiments. In pentane, the alkoxide 5 is moderately stable. Thus, the intermediate 5, prepared by reaction of 1 with tert-butyl formate in pentane, was protonated with water to give the di(hypersilyl)methanol 6 in good yield. The structure of 6 was elucidated by an X-ray crystal structure analysis, which expectedly revealed tremendous distortions of the molecular skeleton. Thus, the spatial demand of the two extended hemispherical (Me3Si)3Si groups forces a widening of the Si-C-Si angle at the central sp3 carbon atom to a value of 135.5°. WILEY-VCH Verlag GmbH, 1997.
View MoreJinan Baozhao Pharmaceutical Co., Ltd
Contact:0086-531-86397156 82371858 82371868
Address:Huaneng Road, Jinan, Shandong ,China
website:http://www.uvchemkeys.com
Contact:0086-021-58785816
Address:RM2607 Building No.1 Guosheng, Lane 388, Zhongjiang Road, Putuo District, Shanghai 200062 China
HangZhou HuaYe Chemical Technology Co.,Ltd
Contact:+86-13505815007
Address:hangzhou
website:https://www.bocsci.com/
Contact:1-631-485-4226
Address:Ramsey Road
website:http://www.hanwayschem.com
Contact:+86-18502787239(whatsapp)
Address:18-1-802, Green Garden, Jianghan District, Wuhan 430023, China
Doi:10.1007/BF00922121
()Doi:10.1002/hlca.19320150156
(1932)Doi:10.1039/c39880000734
(1988)Doi:10.1016/S0031-9422(96)00644-9
(1997)Doi:10.1002/chem.201405684
(2015)Doi:10.1016/S0040-4020(01)88793-7
(1984)