1,2-STEREOCONTROL AND 1,5-STEREOCONTROL IN 5-HEXENYL RADICAL CYCLIZATIONS - COOPERATIVE OR ANTAGONIST EFFECT - CONFRONTATION OF EXPERIMENTAL RESULTS WITH MM2 CALCULATIONS OF TRANSITION-STATES

被引：19

作者：

BERTRAND, MP ^{[1
]}

DERIGGI, I ^{[1
]}

LESUEUR, C ^{[1
]}

GASTALDI, S ^{[1
]}

NOUGUIER, R ^{[1
]}

JAIME, C ^{[1
]}

VIRGILI, A ^{[1
]}

机构：

[1] UNIV AUTONOMA BARCELONA,DEPT QUIM,E-08193 BARCELONA,SPAIN

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1995年 / 60卷 / 19期

关键词：

D O I：

10.1021/jo00124a012

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The cyclofunctionalization of 1,6-dienes 1 and 2 via the addition of tosyl radical allows the analysis of the combined effects of 1,2- and 1,5-stereocontrols on the outcome of 5-hexenyl radical cyclizations. MM2 calculations of transition states agree quite well with the experimental selectivity, i.e., exclusive 1,2-trans control, and predominance of 1,5-cis over 1,5-trans relationship. The addition of TsBr to carbohydrate-derived epimeric dienes 3a and 3b shows that the stereochemistry of the newly formed C-C bond is controlled by the configuration of the C2 center of the radical. 1,5-trans or 1,5-cis selectivity can be achieved depending on the configuration of C2.

引用

页码：6040 / 6045

页数：6

共 39 条

[1]

Allinger N. L., 1980, QCPE, P395

[2] CONFORMATIONAL-ANALYSIS .130. MM2 - HYDROCARBON FORCE-FIELD UTILIZING V1 AND V2 TORSIONAL TERMS [J].

ALLINGER, NL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (25) :8127-8134

[3] REGIO-SELECTIVITY AND STEREO-SELECTIVITY OF ALKENYL RADICAL RING-CLOSURE - A THEORETICAL-STUDY [J].

BECKWITH, ALJ ;

SCHIESSER, CH .

TETRAHEDRON, 1985, 41 (19) :3925-3941

[4]

BECKWITH ALJ, 1991, J ORG CHEM, V56, P5791

[5] TANDEM FREE-RADICAL ALKENE ADDITION-REACTIONS OF ACYL RADICALS [J].

BOGER, DL ;

MATHVINK, RJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (10) :4003-4008

[6] STEREOCHEMISTRY OF FREE-RADICAL ELIMINATIONS ON BETA-PHENYLSULFONYL RADICALS [J].

BOOTHE, TE ;

GREENE, JL ;

SHEVLIN, PB .

JOURNAL OF ORGANIC CHEMISTRY, 1980, 45 (05) :794-797

[7] MM2 MODEL FOR THE INTRAMOLECULAR ADDITIONS OF ACYL-SUBSTITUTED RADICALS TO ALKENES [J].

BROEKER, JL ;

HOUK, KN .

JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (11) :3651-3655

[8] RADICAL CYCLIZATION OF DIENES AND ENYNES USING TOLSO2SEPH [J].

BRUMWELL, JE ;

SIMPKINS, NS ;

TERRETT, NK .

TETRAHEDRON LETTERS, 1993, 34 (07) :1219-1222

[9] THE FREE-RADICAL CYCLIZATION REACTION OF 1,6-DIENES WITH SELENOSULFONATE [J].

CHUANG, CP .

SYNTHETIC COMMUNICATIONS, 1992, 22 (21) :3151-3158

[10]

CHUANG CP, 1990, SYNLETT, P527

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