Total synthesis of (+)-blastmycinone, (-)-litsenolide C1, and related natural trisubstituted lactones via alkynyltungsten compounds

被引:43
作者
Chen, MJ [1 ]
Lo, CY [1 ]
Chin, CC [1 ]
Liu, RS [1 ]
机构
[1] Natl Tsing Hua Univ, Dept Chem, Hsinchu 30013, Taiwan
关键词
D O I
10.1021/jo0002487
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A general method for total synthesis of natural trisubstituted gamma-lactones is developed on the basis of the chemistry of alkynyltungsten compounds. The key step in this approach involves the cycloalkenation of tungsten-eta(1)-(3R,4S)-pent-1-yne-3,4-diol with aldehydes to give;tungsten-oxacarbenium salts, further leading to 3-alkylidene-4-hydroxy-5-methyl-gamma-lacton upon demetalation. This synthetic sequence proceeds well for alkynylaldehydes and the MOM derivative of tungsten-eta(1)-(3R,4S)-pent-1-yne-3,4-diol. The resulting butyrolactone products are transformed into natural trisubstituted butyrolactones including (+)-blastmycinone, (+)-blastmycinolactol, (+)antimycinone, NFX-2, and (+)-isodihydromahubanolide A. By using the same approach based on (R)-ethyl lactate, the natural (-)-litsenolide C-1 can be prepared in a few steps.
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页码:6362 / 6367
页数:6
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