A STEREOSELECTIVE AND ENANTIOSELECTIVE APPROACH TO CLAVULONES FROM TRICYCLODECADIENONE USING FLASH VACUUM THERMOLYSIS

被引:41
作者
ZHU, J
YANG, JY
KLUNDER, AJH
LIU, ZY
ZWANENBURG, B
机构
[1] UNIV NIJMEGEN,NSR,CTR MOLEC STRUCT DESIGN & SYNTH,DEPT ORGAN CHEM,6525 ED NIJMEGEN,NETHERLANDS
[2] CHINESE ACAD SCI,SHANGHAI INST ORGAN CHEM,SHANGHAI 200032,PEOPLES R CHINA
关键词
D O I
10.1016/0040-4020(95)00237-3
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The stereo- and enantioselective synthesis of clavulones 6 and their analogues 48 is described. gamma-Hydroxycyclopentenones (-)-13 and 44 which are key intermediates in this approach, ape obtained from enantiopure endo-tricyclo[5.2.1.0(2,6)]decadienones (+)-14 and (+)-20 in 6 and 8 steps, respectively, Crucial steps are the reductive epoxy ring opening in compounds (+)-25 and 39 to give dap corresponding diols (+)-27 and 40 and the thermal cycloreversion of tricyclodecenones (+)-27 and 41 using the technique of flash vacuum thermolysis (FVT), The synthesis of enantiopure (-)-13 represents a formal total synthesis of clavulones 6. The synthesis of clavulone analogues (-)-48E and (-)-48Z (X= CH2OH) is completed by condensation of 44 with aldehyde 45 followed by elimination of water and removal of the protective THP-group.
引用
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页码:5847 / 5870
页数:24
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