29 α-Phosphorylated Carbanions: Synthetic Features G. STURTZ, B. CORBEL, M. B A B O U L È N E , and J. J. YAOUANC
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Laboratoire de Chimie Hétéroorganique—ERA 612, Faculté des Sciences et Techniques, 6 Avenue Le Gorgeu, 29283 Brest Cédex, France
The study of the chemical reactivity of some phosphates and more specifically, the various possibilities of ester bond rupture, canto some extent be of aid in understanding a few of the mechanisms involved in metabolism effects, while allowing the implementation of new reactions in organic synthesis. For these reasons it seemed of interest to attempt to create an α-carbanion from a phosphoric acid derivatives 1 ©
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The following question could, for example, be put forward as to whether a carbenic or carbenoic entity would be yielded. By selecting certain terpenic phosphates as a substratum , biosynthesis advantages could be brought out by avowing the "natural" possibility of creating this carbanion in a terpenic pyrophosphate, for example ; this to our knowledge has never been brought up in reactions with respect to these compounds. First (1), we have shown that 0-benzylic phosphoric acid derivatives 2 treated with a strong base produced phosphate carbanions which immediately rearranged into α-hydroxy phosphonate oxanions 3 .
3 0097-6156/81/0171-0149$05.00/0 © 1981 American Chemical Society In Phosphorus Chemistry; Quin, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
150
PHOSPHORUS CHEMISTRY
Using
two equivalents o f η b u t y l l i t h i u m one can i s o l a t e benzoine.
The presence of p r o p i o n i c a c i d i n small q u a n t i t y beside the α-hydroxy phosphonamide 5_ when 0 - a l l y l i c phosphoramide 4_ i s t r e a t e d by one e q u i v a l e n t of η-Butyllithium has r e q u i r e d the a n a l y s i s o f the c o n d i t i o n s o f i t s formation ( 2 ) . l)n-Bu L i THF, f(CH ) N)
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-CH=CH 2
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H
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%
+ CH CH C0 H 3
2
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10% The mesomeric form _6 Β e x p l a i n s the o b t e n t i o n o f t h i s a c i d : H [ ( C H ) N | P-0-CH -CH=CH ~ °^ J ( C H ) N J P-è-CH=CH n
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)
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-
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6 A -
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C H
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6
Β
m - S M- C H
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3
(R 0)
R I 2 R Ρ - 0 - b = CH - SR 0 i l
Indeed i n the same experimental c o n d i t i o n s the g e r a n y l phosphate b r i n g s the formation of an α-hydroxy phosphonate which can give the c i t r a l . By u s i n g a double q u a n t i t y of base, we get c i t r o n e l l i c a c i d and we know that t h i s type of compound i s found i n some p l a n t s . So we may consider that i n the f i e l d of a b i o l o g y enzymatic s y s tem would e x i s t , which could lead from g e r a n y l pyrophosphate to such t r a n s p o s i t i o n s . This hypothesis would e x p l a i n the presence of these compounds i n t o some p l a n t s . LITERATURE CITED
1. STURTZ, G. and CORBEL, B. C.R. Acad. Sc. Paris, série C t. 276, 1973, p 1807. 2. STURTZ, G. and CORBEL, B. C.R. Acad. Sc. Paris, série C t. 277, 1973, p 395. 3. STURTZ, G., CORBEL, B. and PAUGAM, J.P. Tetrahedron Letters, 1976, P 47. 4. STURTZ, G., YAOUANC, J.J., KRAUSZ, F. and LABEEUW, B. Synthesis, 1980,P289. 5. BABOULENE, M. and STURTZ, G. Journal of Organometallic Chemistry, 1979, p 27. 6. TANAKA, K., UNEME, Η., ΟΝΟ, Ν. and KAJI, A. Chemistry Letters 1979, P 1039. R E C E I V E D July 7,
1981.
In Phosphorus Chemistry; Quin, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
