(Z)-(E) INTERCONVERSION OF OLEFINS BY THE ADDITION-ELIMINATION SEQUENCE OF THE (TMS)(3)SI. RADICAL

被引：39

作者：

CHATGILIALOGLU, C ^{[1
]}

BALLESTRI, M ^{[1
]}

FERRERI, C ^{[1
]}

VECCHI, D ^{[1
]}

机构：

[1] UNIV NAPLES FEDERICO II,DIPARTIMENTO CHIM ORGAN & BIOL,I-80134 NAPLES,ITALY

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1995年 / 60卷 / 12期

关键词：

D O I：

10.1021/jo00117a038

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Tris(trimethylsilyl)silyl radical is effective in isomerizing either acyclic or cyclic olefins by an addition-elimination sequence. The E/Z ratio after equilibration generally reflects the thermodynamic stability of (Z)- and (E)-alkenes. It has been shown for (E)- and (Z)-hexen-1-ol that equilibration (Z/E = 18/82) is reached with the (TMS)(3)Si . radical in 10 h at 80 degrees C, whereas with PhS . and Bu(3)Sn . radicals the same isomeric composition is reached in 1 and 4 h, respectively. In cyclic systems like (Z)-cyclododecene the ratio of Z/E = 46/54 is reached in 8 h, while with PhS . and Bu(3)Sn . it is much slower. An explanation of this phenomenon has been advanced. Additional information on the impact of this addition-elimination methodology in organic synthesis is given.

引用

页码：3826 / 3831

页数：6

共 67 条

[1] CATALYSED ISOMERISATION REACTIONS OF CYCLODODECA-1,5,9-TRIENE [J].

ATTRIDGE, CJ ;

MADDOCK, SJ .

JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1971, (18) :2999-&

[2] TRIS(TRIMETHYLSILYL)SILANE AS A RADICAL-BASED REDUCING AGENT IN SYNTHESIS [J].

BALLESTRI, M ;

CHATGILIALOGLU, C ;

CLARK, KB ;

GRILLER, D ;

GIESE, B ;

KOPPING, B .

JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (02) :678-683

[3]

BENNETT SW, 1968, J ORGANOMET CHEM, V15, P17

[4] HEATS OF FORMATION OF RADICALS AND MOLECULES BY A PHOTOACOUSTIC TECHNIQUE [J].

BURKEY, TJ ;

MAJEWSKI, M ;

GRILLER, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (09) :2218-2221

[5] RATE CONSTANTS AND ARRHENIUS PARAMETERS FOR THE REACTIONS OF PRIMARY, SECONDARY, AND TERTIARY ALKYL RADICALS WITH TRI-NORMAL-BUTYLTIN HYDRIDE [J].

CHATGILIALOGLU, C ;

INGOLD, KU ;

SCAIANO, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (26) :7739-7742

[6] ABSOLUTE RATE CONSTANTS FOR THE ADDITION OF TRIETHYLSILYL RADICALS TO VARIOUS UNSATURATED-COMPOUNDS [J].

CHATGILIALOGLU, C ;

INGOLD, KU ;

SCAIANO, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (10) :3292-3296

[7] ORGANOSILANES AS RADICAL-BASED REDUCING AGENTS IN SYNTHESIS [J].

CHATGILIALOGLU, C .

ACCOUNTS OF CHEMICAL RESEARCH, 1992, 25 (04) :188-194

[8]

CHATGILIALOGLU C, 1988, B SOC CHIM FR, P298

[9] RATE CONSTANTS AND ARRHENIUS PARAMETERS FOR THE REACTIONS OF SOME CARBON-CENTERED RADICALS WITH TRIS(TRIMETHYLSILYL)SILANE [J].

CHATGILIALOGLU, C ;

DICKHAUT, J ;

GIESE, B .

JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (22) :6399-6403

[10]

CHATGILIALOGLU C, 1994, CHEM TRIPLE BOND SC2, V2, pCH16

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