TY - CHAP
T1 - The Synthesis of Transient Silenes using the Principle of the Peterson Reaction
AU - Krempner, Clemens
AU - Reinke, Helmut
AU - Oehme, Hartmut
N1 - Publisher Copyright:
© 2008 VCH Verlagsgesellschaft mbH. All rights reserved.
Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.
PY - 2008/6/10
Y1 - 2008/6/10
N2 - Deprotonation of 1-hydroxyalkyltris(trimethylsilyl)silanes, (Me3Si)3Si-C(OH)R1R2 (1) with methyl lithium in ether at low temperature leads to transient silenes, (MeSi2)2Si=CR1R2 (2a: R1 = R2 = Me; 2b: R1 = H, R2 = tBu; 2c: R1 = H; R2 = Mes), which dimerize in absence of trapping agents to give 1-isopropenyl-2-isopropyl-1,1,2,2-tetrakis-(trimethylsilyl)disilane 3, (E)-3,4-di-/butyl-1,1,2,2-tetrakis(trimethylsilyl)-1,2-disilacyclo-butane 4 and (E)-1,2,3,8α-tetrahydro-l-mesityl-5,7,8α-trmiethyl-2,2,3,3-tetrakis(trimethyl-silyl)-2,3-disilanaphthalene 5, resp. Deprotonation of 1a-1c with excess organolithium reagents leads to trisilanes 6, the addition products of the nucleophilic organolithium compounds across the SiC bond of the intermediate silenes 2a-2c. Compounds 2b and 2c can also be trapped with 2,3-dimethyl-1,3-butadiene to give the silacyclohex-3-enes 9a and 9b. The interaction of 1a-1c with methyllithium or sodium hydride in THF causes a 1,3-Si-O trimethylsilyl migration resulting in formation of trimethylsiloxybis(trimethylsilyl)silyl-alkanes (Me3Si)2SiH-C(OSiMe3)R1R2 10a-10c. Deprotonation of 1c with methylmagnesium-bromide in THF gives (E)-2,4-dimesityl-1,1,3,3-tetrakis(trimethylsilyl)-1,3-disilacyclobutane 12
AB - Deprotonation of 1-hydroxyalkyltris(trimethylsilyl)silanes, (Me3Si)3Si-C(OH)R1R2 (1) with methyl lithium in ether at low temperature leads to transient silenes, (MeSi2)2Si=CR1R2 (2a: R1 = R2 = Me; 2b: R1 = H, R2 = tBu; 2c: R1 = H; R2 = Mes), which dimerize in absence of trapping agents to give 1-isopropenyl-2-isopropyl-1,1,2,2-tetrakis-(trimethylsilyl)disilane 3, (E)-3,4-di-/butyl-1,1,2,2-tetrakis(trimethylsilyl)-1,2-disilacyclo-butane 4 and (E)-1,2,3,8α-tetrahydro-l-mesityl-5,7,8α-trmiethyl-2,2,3,3-tetrakis(trimethyl-silyl)-2,3-disilanaphthalene 5, resp. Deprotonation of 1a-1c with excess organolithium reagents leads to trisilanes 6, the addition products of the nucleophilic organolithium compounds across the SiC bond of the intermediate silenes 2a-2c. Compounds 2b and 2c can also be trapped with 2,3-dimethyl-1,3-butadiene to give the silacyclohex-3-enes 9a and 9b. The interaction of 1a-1c with methyllithium or sodium hydride in THF causes a 1,3-Si-O trimethylsilyl migration resulting in formation of trimethylsiloxybis(trimethylsilyl)silyl-alkanes (Me3Si)2SiH-C(OSiMe3)R1R2 10a-10c. Deprotonation of 1c with methylmagnesium-bromide in THF gives (E)-2,4-dimesityl-1,1,3,3-tetrakis(trimethylsilyl)-1,3-disilacyclobutane 12
UR - http://www.scopus.com/inward/record.url?scp=84959145577&partnerID=8YFLogxK
U2 - 10.1002/9783527620777.ch46a
DO - 10.1002/9783527620777.ch46a
M3 - Chapter
AN - SCOPUS:84959145577
SN - 9783527323470
SP - 389
EP - 398
BT - Organosilicon Chemistry Set
PB - Wiley
ER -