NUCLEOPHILIC ADDITIONS TO TRICYCLODECADIENONE EPOXIDES - THE PAYNE REARRANGEMENT OF ALPHA,BETA-EPOXYCYCLOPENTANOLS CONTAINED IN A RIGID TRICYCLIC SYSTEM

被引：11

作者：

DOLS, PPMA ^{[1
]}

ARNOUTS, EG ^{[1
]}

ROHAAN, J ^{[1
]}

KLUNDER, AJH ^{[1
]}

ZWANENBURG, B ^{[1
]}

机构：

[1] CATHOLIC UNIV NIJMEGEN,CTR MOLEC STRUCT DESIGN & SYNTH,DEPT ORGAN CHEM,NSR LAB,6525 ED NIJMEGEN,NETHERLANDS

来源：

TETRAHEDRON | 1994年 / 50卷 / 11期

关键词：

D O I：

10.1016/S0040-4020(01)87027-7

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Organometallic reagents add regio- and stereoselectively from the convex exo-face to the carbonyl function of exo-4,5-epoxytricyclodecenones 5 and 8 to give tricyclic exo-epoxy-endo-alcohols 6 and 9, respectively. These initial adducts can undergo a Payne rearrangement to give inverted endo-epoxy-exo-alcohols 7 and 10, respectively. The rearrangement is dependent on substrate, experimental conditions and type of organometallic reagent. Reduction of 6 and 7 with lithium aluminum hydride yields the same tricyclic trans-1,3-diols 20. It is show that reduction of 6 with lithium aluminum hydride proceeds via slow Payne rearrangement of its alkoxide 11b to inverted alkoxide 12b, followed by rapid addition of hydride to C-4 from the exo-face.

引用

页码：3473 / 3490

页数：18

共 24 条

[1] CYCLOPENTADIENONE EPOXIDE - SYNTHESIS AND PHOTOCHEMISTRY [J].