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RING C T R A N S F O R M A T I O N S
P O D O C A R P I C A C I D
A Thesis
presented t o the University of Auckland f o r the Degree of
Doctor of Philosophy
Alan W. Missen
University of Auckland September 1971
ABSTRACT
INTRODUCTION
Reduced Ring C Transformations Aromatic Ring C Transformations
DISCUSSION
Reduced Ring C Transformations
Aromatic Ring C Transformations: synthesis of Methyl (+) -1 3-methoxypodocarpa-8,11,13-trien-l9-oate
Further reactions of methyl
(+)
-1 3-methoxypodocarpa- 8,11,13-trien-19-sateAttempted Synthesis of Methyl 14-methoxypodocarpa- 8, I I ,I 3-trien-I 9-oate
EXPERIMENTAL
DIAGRAMS
This 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 te r p e n o i d n a t u r a l product
,
1 2-hydrorypodocarpa-8,
1 1,
1 3 - t r i m I 9-oic acid* ( p o d o c a r p i c a c i d ) ( I ) . I n p a r t i c u l a r 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 for t h e s y n t h e s i s of o p t i c a l l y active s t e r o i d s and t e r p e n o i d s .An i n v e s t i g a t i o n h a s been c a r r i e d out on t h e Birch r e d u c t i o n of 1 2-methoxypodocarpa-8,11
,
I 3-tricn-19-01 (8),
'and c o n d i t i o n s f o r t h e optimum formation of t h e k e t o n i c products ( 1 0) and ( 1 2) are suggested.T h e enones (25) and (26) have been syntllcsised from
12-hydrowpodocarpa-8? 11
,
1 3 4 r i e n - 1 9 - o i c 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-8,11,1 3-trim-1 9 - 0 ( 3 ) has been converted i n
z.
60% y i e l d t o the d e x t r o r o t a t o r y C 13 methyl e t h e r which has then been reduced good y i e l d t h eP o t e n t i a l r o u t e s f o r conversion of t h e enones ( 2 5 )
,
(26), and (1 63)*
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 ~ o r r ~ n u n i c a t i o n t o P r o f e s s o r R. C. ~ a m b i e ) i n ((The Cornnton and Systematic Nomenclature of C y c l i c Di terpenes",
3rd Revision, Oct. 1966, t o be s u b m i t t e d t o t h e IUPAC Commission on Organic N o m e n c l a t ~ r e ( s ~ fL:!4?,
i n t o s t c r o i d a l analogues a r e 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 methyl ether ( 6 2 ) i n t o an i n t e r m c d i z t c (176) s u i t a b l e for t h e synthesis of
(+)
-a-onocerin ( 8 0 ) have been i n v e s t i g a t e d .A p r e l i m i n a r y study on t h e synthesis of the C 14 p h e n o l ( 1 9 0 ) or its m e t h y l e t h e r (191) is a l s o r e p o r t e d .
