HOMOLYTIC SUBSTITUTION-REACTION AT A SILICON ATOM

被引：46

作者：

KULICKE, KJ ^{[1
]}

CHATGILIALOGLU, C ^{[1
]}

KOPPING, B ^{[1
]}

GIESE, B ^{[1
]}

机构：

[1] UNIV BASEL,INST ORGAN CHEM,ST JOHANNS RING 19,CH-4056 BASEL,SWITZERLAND

来源：

HELVETICA CHIMICA ACTA | 1992年 / 75卷 / 03期

关键词：

D O I：

10.1002/hlca.19920750327

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Tris(trimethylsilyl)silane (2) is an efficient hydrosilylating agent of 1,6-dienes 1 operating via a free-radical chain mechanism. The intermediate alkyl radical 3 attacks the second olefinic bond of the diene 1 and forms cyclopentylalkyl radical 4. Using a low concentration of the hydrogen donor 2, a radical substitution reaction at the Si-center of cis-4 occurs and yields the bicyclic silane 6. The rate of this homolytic substitution at the Si-atom is 2.4 . 10(5) s-1 (80-degrees).

引用

页码：935 / 939

页数：5

共 12 条

[1] C-13-NMR STUDY OF SUBSTITUENT EFFECTS OF CHEMICAL-SHIFTS IN METHYL TETRAHYDROFURANS
ACCARY, A
HUET, J
INFARNET, Y
DUPLAN, JC
[J]. ORGANIC MAGNETIC RESONANCE, 1978, 11 (06): : 287 - 290
[2] REACTIONS OF TRIPLET CARBONYL-COMPOUNDS AND NITRO-DERIVATIVES WITH SILANES
ALBERTI, A
DELLONTE, S
PARADISI, C
ROFFIA, S
PEDULLI, GF
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (03) : 1123 - 1129
[3] TRIS(TRIMETHYLSILYL)SILANE AS A RADICAL-BASED REDUCING AGENT IN SYNTHESIS
BALLESTRI, M
CHATGILIALOGLU, C
CLARK, KB
GRILLER, D
GIESE, B
KOPPING, B
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (02) : 678 - 683
[4] RATE CONSTANTS AND ARRHENIUS PARAMETERS FOR THE REACTIONS OF SOME CARBON-CENTERED RADICALS WITH TRIS(TRIMETHYLSILYL)SILANE
CHATGILIALOGLU, C
DICKHAUT, J
GIESE, B
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (22) : 6399 - 6403
[5] DICKHAUT J, 1991, ORG SYNTH, V70, P164
[6] INGOLD KU, 1971, FREE RADICAL SUBSTIT
[7] KALINOWSKI HO, 1984, 13C SPEKTROSKOPIE, P104
[8] KULICKE KJ, 1990, SYNLETT, P91
[9] ZIRCONIUM-MEDIATED RING CONSTRUCTION FROM DIENES - REMARKABLE EFFECT OF LIGANDS ON STEREOCHEMISTRY
NUGENT, WA
TABER, DF
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (16) : 6435 - 6437
[10] PYROLYSIS OF ORGANODISILANES
SAKURAI, H
KOH, R
HOSOMI, A
KUMADA, M
[J]. BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1966, 39 (09) : 2050 - +

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