Tandem radical mediated 5-exo-trig, 6-endo-dig cyclization. Stereoselectivity, alpha-trimethylsilyl effect and the product spread .4.

被引:17
作者
Breithor, M [1 ]
Herden, U [1 ]
Hoffmann, HMR [1 ]
机构
[1] UNIV HANNOVER,DEPT ORGAN CHEM,D-30167 HANNOVER,GERMANY
关键词
D O I
10.1016/S0040-4020(97)00519-X
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Stereochemistry and mechanism of the title reaction have been investigated. The reaction proceeds well in the (S) series. In the epimeric (R) series a product spread is usually observed. In either series olefin configuration is lost (7 examples), consistent with a freely rotating exocyclic radical intermediate. An alpha-trimethylsilyl group at the olefinic terminus enhances the selectivity of the radical cascade Spectroscopic evidence and MMX calculations suggest that the tandem annulation products of the (S) series are favoured thermodynamically, being more stable than those of the (R) series. Pyranoside (R)G2a is frozen in a half chair conformation. (C) 1997 Elsevier Science Ltd.
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收藏
页码:8401 / 8420
页数:20
相关论文
共 20 条
[1]  
ALBRECHT U, 1992, ANGEW CHEM INT EDIT, V31, P903
[2]  
Albrecht U., 1992, ANGEW CHEM, V104, P903
[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]   DIASTEREOSELECTIVE SYNTHESIS OF FUNCTIONALIZED 9-RING ETHERS (OXONINS) [J].
BRANDES, A ;
HOFFMANN, HMR .
TETRAHEDRON, 1995, 51 (01) :145-154
[5]  
BREITHOR M, 1997, KRISTALLOGRAFIYA, V212, P251
[6]   SYNTHESIS OF MEDIUM RING ETHERS .2. SYNTHESIS OF THE FULLY SATURATED CARBON SKELETON OF LAURENCIA NON-TERPENOID ETHER METABOLITES CONTAINING 7-MEMBERED, 8-MEMBERED AND 9-MEMBERED RINGS [J].
CARLING, RW ;
CLARK, JS ;
HOLMES, AB .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1992, (01) :83-94
[7]   NEW INSIGHTS REGARDING THE CYCLIZATION PATHWAY FOR STEROL BIOSYNTHESIS FROM (S)-2,3-OXIDOSQUALENE [J].
COREY, EJ ;
VIRGIL, SC ;
CHENG, HM ;
BAKER, CH ;
MATSUDA, SPT ;
SINGH, V ;
SARSHAR, S .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (47) :11819-11820
[8]   RADICAL-INITIATED POLYOLEFINIC CYCLIZATIONS IN LINEAR TRIQUINANE SYNTHESIS - MODEL STUDIES AND TOTAL SYNTHESIS OF (+/-)-HIRSUTENE [J].
CURRAN, DP ;
RAKIEWICZ, DM .
TETRAHEDRON, 1985, 41 (19) :3943-3958
[9]   RADICAL-INITIATED POLYOLEFINIC CYCLIZATIONS IN CONDENSED CYCLOPENTANOID SYNTHESIS - TOTAL SYNTHESIS OF (+/-)-DELTA9(12)-CAPNELLENE [J].
CURRAN, DP ;
CHEN, MH .
TETRAHEDRON LETTERS, 1985, 26 (41) :4991-4994
[10]   TANDEM RADICAL APPROACH TO LINEAR CONDENSED CYCLOPENTANOIDS - TOTAL SYNTHESIS OF (+/-)-HIRSUTENE [J].
CURRAN, DP ;
RAKIEWICZ, DM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (05) :1448-1449