Synthesis of functionalized bicyclo[3.2.1]octa-2,6-dienes by thermal rearrangement of substituted 6-exo-(1-alkenyl)bicyclo[3.1.0]hex-2-ene systems

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Abstract
Thermolysis of each of the enol silyl ethers 31-35 affords, cleanly and efficiently, the bicyclo[3.2.1]octadienes 36-40, respectively. Similarly, thermal rearrangement of the enol silyl ether 50 provides the diene 51. Hydrolysis of 36, 37, and 39, and decarbomethoxylation of the resultant keto esters 41, 42, and 44, gives the ketones 46-48, respectively. The ketone 46 is also obtained by acid hydrolysis of 51. Conversion of 6-methyl-1-hepten-4-yn-3-ol (56) into the enol ether 63 is described. Thermolysis of 63 gives 64, which, upon acid hydrolysis, affords 65. Thermolysis of the enones 68 and 69 produces the bicyclic dienones 70 and 71, respectively. On the other hand, thermolysis of 73 and 74, derived from the enone 69, provides the C-8 exo substituted bicyclo[3.3.1]octa-2,6-dienes 75 and 76, which are transformed smoothly, by acid hydrolysis, into the ketones 77 and 78, respectively.

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