TRANS-ANNULAR CYCLIZATION AS A STRATAGEM IN SYNTHESIS - A TOTAL SYNTHESIS OF (+/-)-PENTALENENE
TRANS-ANNULAR CYCLIZATION AS A STRATAGEM IN SYNTHESIS - A TOTAL SYNTHESIS OF (+/-)-PENTALENENE
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DOI：
10.1016/s0040-4020(01)87743-7
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发表时间：
1987-01-01
期刊：
影响因子：
2.1
通讯作者：
TEAGUE, SJ
中科院分区：
文献类型：
--
作者：
PATTENDEN, G;TEAGUE, SJ
三醌型倍半萜（. ±.）在链霉菌中发现的并环戊二烯（1），是基于双环[6.3.0]十一碳二烯（7）在三氟化硼醚合物存在下的跨环环化。使用独特的分子内[2+2]光环化加成- Grob断裂序列从甲硅烷基烯醇醚（36）制备双环[6.3.0]十一碳二烯（7），得到（8）[即（36）→(37)和（38）]，然后烯化成（40）并在三水合铑存在下异构化。
A total synthesis of the triquinane sesquiterpene (.+-.)-pentalenene (1) found in Streptomyces, bases on transannular cyclisation of the bicyclo [6.3.0] undecadiene (7) in the presence of boron trifuluoride etherate is described. The bicyclo [6.3.0] undecadiene (7) was elaborated from the silyl enol ether (36) using a unique intramolecular [2+2]photocycloaddition - Grob fragmentation sequence leading to (8) [viz (36) .fwdarw. (37) and (38)], followed by olefination to (40) and isomerisation in the presence of rhodium trichloride trihydrate.