Enantiospecific total synthesis of (-)-4-thiocyanatoneopupukeanane |
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Authors: | Srikrishna A Gharpure S J |
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Affiliation: | Department of Organic Chemistry, Indian Institute of Science, Bangalore 560 012, India. ask@orgchem.iisc.ernet.in |
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Abstract: | Enantiospecific synthesis of the natural enantiomer of the marine sesquiterpene (-)-4-thiocyanatoneopupukeanane (6) is described. The bicyclo[2.2.2]octanecarboxylate 14, obtained from (R)-carvone via Michael-Michael reaction, was transformed into neopupukeananedione 12 by employing rhodium acetate catalyzed intramolecular C-H insertion of the diazo ketones 16 or 19 as the key reaction. Regioselective deoxygenation of the C-2 ketone transformed the dione 12 into neopupukean-4-one 10. Alternately, the keto ester 18 was also transformed into neopupukean-4-one 10 via regioselective deoxygenation of the ketone in 18 followed by intramolecular rhodium carbenoid C-H insertion of the diazo ketone 31. Finally, neopupukean-4-one 10 was transformed into (-)-4-thiocyanatoneopupukeanane 6 via the alcohol 32 and the mesylate 33. |
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