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T h i s t h e s i s describes f u r t h e r s t u d i e s on the u t i l i s a t i o n of t h e d i t e r p e n o i d n a t u r a l p r o d u c t , 12-hydro~jpodocarpa-8,11,13-trien- 19-oic acid* ( p o d o c a r p i c a c i d ) ( 1 ) . I n p a r t i c u l u it d e s c r i b e s t r a n s f o r m a t i o n s of t h e C-ring t o g i v e s u i t a b l e i n t e r m e d i a t e s f o r t h e s y n t h e s i s of o p t i c a l l y active steroids and t e r p e n o i d s .
A n i n v e s t i g a t i o n has been c a r r i e d out on the B i r c h r e d u c t i o n of 12-methoxypodocarpa-8,11, I 3- tricn-19-01 (8)
,
,md c o n d i t i o n s f o r the optimum formation of t h e k e t o n i c products (1 0) and ( I 2) are suggested.T h e enones (25) and ( 2 6 ) have been synthesised from
1 2-hydroxypodocarpa-8,11,13-trien-19-oic a c i d ( I
)
by sequences involving r e d u c t i o n of t h e aromatic r i n g followed by r i n g C transfcrmations.Methyl 12-hydroxypodocarpa-8,11,13-tricn-l 9 - o a t ( 3 ) has been converted i n
z.
60% yield t o the d e x t r o r o t a t o r y C 1 3 methylether (62), w h i c h h a s then been reduced in good y i e l d t o t h e enone (1 63).
P o t e n t i a l routes f o r conversion of the enones (25), (26), and (163)
*
The numbering system used throughout t h i s t h e s i s i s t h a t proposed by J.W. Rowe ( p e r s o n a l corrJnunication t o P r o f e s s o r R. C. ~ a m b i e ) i n "The Comon and Systematic Nomenclature of Cyclic Diterpenes",
3rd Revision, Oct. 1968, t o be submitted t o t h e IUPAC Commission on Organic Nomenclature (s'- ! k k ? ,
ii.
into s t e r o i d a l analogues are described.
I n i t i a l s t e p s i n the t r a n s f o r m a t i o n of the C 13 m e t h y l e t h e r ( 6 2 ) into an interrncdi3.t~ (176) s u i t a b l e f o r t h e s y n t h e s i s of
(+)-oronocerin ( 8 0 ) have been i n v e s t i g a t e d .
A preliminary s t u d y on t h e s y n t h e s i s of t h e C 14 p h e n o l ( 1 9 0 ) or its m e t h y l e t h e r (1 9 1 ) is a l s o r e p o r t e d .
