Enantiospecific total synthesis of (−)-4-thiocyanatoneopupukeanane

Srikrishna, A. ; Gharpure, Santosh J. (2001) Enantiospecific total synthesis of (−)-4-thiocyanatoneopupukeanane Journal of Organic Chemistry, 66 (12). pp. 4379-4385. ISSN 0022-3263

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Official URL: http://pubs.acs.org/doi/abs/10.1021/jo0102765

Related URL: http://dx.doi.org/10.1021/jo0102765


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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Deposited On:15 Jul 2011 11:41
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