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The total synthesis of natural products Volume 2 by John ApSimon

25 February 2017 adminGeneral Reference

By John ApSimon

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Extra info for The total synthesis of natural products Volume 2

Example text

C H ~ C O C H ~ C O O C ~ H S (NaNH2) ___c p BrCH2CH=C 'CH CH~CO-CH-COOC~HS 3 I CH2CH=C /CH3 \ 3 133 - Wittig ___c CH3 I CH2CH=C p \ 129 - 3 CH3 Prenyl bromide can, i n f a c t , be coupled t o g i v e t h e lavandulyl s k e l e t o n d i r e c t l y ; z i n c c h l o r i d e i n carbon t e t r a c h l o r i d e y i e l d s t h e dibromide (=) t h a t l o s e s one molecule of hydrogen bromide i n t h e presence of potassium a c e t a t e i n t h e second bromine being r e p l a c e d by acetic acid ( t o hydroxyl v i a t h e corresponding Grignard r e a g e n t .

When c r o t y l a l c o h o l was u s e d i n s t e a d o f t h e b u t y n o l , d i h y d r o t a g e t o n e (2) i s o b t a i n e d a s the major p r o d u c t ( 6 0 % ) of t h e m i x t u r e , t h e remainder c o n s i s t i n g o f t h e two stereomers o f t h e u n d e s i r e d isomer ( a s ) , t h e l a t t e r t h r e e p r o d u c t s b e i n g d i f f i c u l t t o separate79 (z), 5. SUBSTANCES DERIVED FROM CHRYSANTHEMIC A C I D I n 1965, Bates and P a k n i k a r l Z 3 showed how i t w a s possible t o d e r i v e t h e s k e l e t o n s o f a number o f n a t u r a l l y o c c u r r i n g monot e r p e n e s from t h a t of n a t u r a l t r a n s - c h r y s a n t h e m i c a c i d (%) by f i s s i o n of t h e v a r i o u s bonds o f t h e c y c l o p r o p a n e r i n g .

Were able to make the dicarboxylic acid [pyrethric acid (149, R = H) also a constituent of pyrethrum] from 2,5-dimethylhexa-2,4-dienoic acid (150) 76 (z, ’ . - N~CHCOOC~HSR O I 148 - H I O I C \ 90a - \ H M R T & H I’ H 90b - *For a review of the earlier work in this field, see the description of the chemistry of the pyrethrins by Crombie and Elliott. A similar s nthesis using the t-butyl ester has also been described. 17x 50 The S y n t h e s i s of Monoterpenes N2CHCOOR Hydrolyse , e t c . ____L H' COOH 149 - 150 - I t was found by J u l i a e t a l .

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