Studies in terpenoids-XVII. Synthesis of 7-hydroxycadalenal and some related naturally occurring sesquiterpenoids

The synthesis and facile elaboration of 7-methoxycalamenal (4b) to four naturally occurring phenolic sesquiterpenoids, 7-hydroxycalamenene (4e), 7-hydroxycadalene (13e), 7-hydroxycalamenal (4f), and 7-hydroxycadalenal (13f) are described.

Reaction of benzisoxazolium cations with cyclic β-diketones

Reaction of 2-ethylbenzisoxazolium fluoborate (III) with dimedone, dihydroresorcinol, 2-methyldihydroresorcinol and 2-methylcyclopentane-1,3-dione in the presence of base leads to the formation of amides VIII, XI, X and XIII respectively, via the benzoketoketenimine intermediate (IX) and an intramolecular migration. The 7-hydroxy-2-ethylbenzisoxazolium salt (IV) gives the amide (XIV) by double migration. Amides VIII, XI, X and XIII undergo intramolecular Michael reaction to furnish the benzoxazinones (XVI, XVIII, XVII and XXVI). Stereochemistry of this addition is discussed and the conformation in which the CN bond at C-1′ is attached equatorially to the cyclohexanone ring is assigned to the Spirans (XX, XXX and XXVIII). Effect of acids and bases on the amide (VIII) and the spiran (XVI) is described.

Studies in stereochemistry—I : Stereospecific routes to trans- anti- and cis- syn-Δ8-dodecahydrophenanthrenes

Reduction of trans-1-oxo-7-methoxy-1,2,3,4,9,10,11,12-octahydrophenanthrene (XI) by lithium tri-t-butoxyaluminohydride gave trans-1β-hydroxy-7-methoxy-1,2,3,4,9,10,11,12-octahydrophenanthrene (XII) which on lithium-liquid ammonia reduction gave trans-anti-1β-hydroxy-7-oxo-Δ8(14)-dodecahydrophenanthrene (XIII). Reduction of cis-1-oxo-7-methoxy-1,2,3,4,9,10,11,12-octahydrophenanthrene (XV) by sodium borohydride gave cis-1α-hydroxy-7-methoxy-1,2,3,4,9,10,11,12-octahydrophenanthrene (XVI) which on lithium-liquid ammonia reduction gave cis-syn-1α-hydroxy-7-oxo-Δ8(14)-dodecahydrophenanthrene (XVII).

Studies in sesquiterpenes-XVI. Zerumbone, a monocyclic sesquiterpene ketone

The structure, previously assigned to zerumbone, has been found to be untenable. The ketone has been shown to be monocyclic containing three ethylenic linkages, and has been further correlated with humulene. Results from ozonolysis, and base-catalysed cleavage allowed the compound to be formulated as 2,6,9,9-tetramethyl-2,6,10-cyclo-undecatrien-1-one.