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Total Synthesis of (±)‐Clovene. On the Stereoelectronic Requirements of the α‐Alkynone Cyclisation
Author(s) -
Ackroyd John,
Karpf Martin,
Dreiding André S.
Publication year - 1984
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19840670735
Subject(s) - chemistry , carbene , thermal decomposition , bicyclic molecule , selectivity , adamantane , carboxylic acid , stereochemistry , carboxylate , medicinal chemistry , organic chemistry , catalysis
The synthesis of the sequiterpenoid tricyclic hydrocarbon (±)‐cleovene ( 1 ) by application of the α‐alkynone cyclisation is described. The starting bicyclic carboxylic acid 2 was obtained from ethyl 3‐methyl‐2‐oxocyclohexane‐1‐carboxylate by modified known methods (24%) and converted to the α‐alkynone 3 (86%). The thermolysis of 3 in the gas phase at 620° selectively produced the tricyclo[6.3.1.0 1,5 ] dodecenone 4 (80%) which was converted to 1 (37%) by conventional procedures. The selectivity of the α‐alkynone cyclisation is discussed in terms of the stereoelectronic requirements (coplanarity factor) of the carbene insertion. In order to throw further light on the importance of this factor, the (1‐adamantyl) alkynone 16 was synthesised from adamantane‐1‐carboxylic acid (78%) and subjected to thermolysis at 620°. Since this led to the tetracyclo[6.3.1.1.1 3,10 .0 3,7 ]tridecenones 17 and 18 (together 72%), we conclude that the planar carbene insertion transition state, while preferred, is not a stringent requirement.