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The First Synthesis of (−)‐Asperpentyn and Efficient Syntheses of (+)‐Harveynone, (+)‐Epiepoformin and (−)‐Theobroxide
Author(s) -
Barros M. Teresa,
Maycock Christopher D.,
Ventura M. Rita
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20001103)6:21<3991::aid-chem3991>3.0.co;2-v
Subject(s) - enantioselective synthesis , chemistry , stereoselectivity , stereochemistry , stille reaction , enantiopure drug , organic chemistry , catalysis
Abstract A generally applicable strategy for the synthesis of a range of polyoxygenated cyclohexane natural products has been developed. The enantioselective syntheses of (−)‐theobroxide, a polyoxygenated cyclohexane natural compound with potent growth inducing properties in potato microtubers has been achieved via a 1,2 O ‐silyl migration between trans ‐hydroxyl groups and a remote hydroxyl directed epoxidation of an enone derived from quinic acid. A thus derived α‐iodoenone was subjected to Stille coupling with tetramethylstannane to afford the first title compound. A similar strategy enabled a route to the complete asymmetric synthesis of the acetylenic phytotoxin (+)‐harveynone. By selective reduction of (−)‐theobroxide, (+)‐epiepoformin was also prepared in enantiopure form and similarly, stereoselective reduction of (+)‐harveynone completed the first enantioselective synthesis of (−)‐asperpentyn, another natural compound with antimicrobial activity.