10
Downloaded by OHIO STATE UNIV LIBRARIES on October 14, 2014 | http://pubs.acs.org Publication Date: November 11, 1981 | doi: 10.1021/bk-1981-0171.ch010
Reactions of Aziridines, 4-Oxazolines, and Their Derivatives with Alkylidene Phosphoranes and Phosphorus(III) Nucleophiles M. VAULTIER and R. CARRIÉ Groupe de Physicochimie Structurale, ERA CNRS N° 389, Université de Rennes, 35042 Rennes Cédex, France
The aziridines 1a, b and the oxazolines 2c, 2d and 2e, bearing at least one electron withdrawing group are thermically i n equilibrium with the corresponding azomethine ylids 3 which may be protonated to give the functional iminium salts 4 according to the following scheme (1, 2) :
0097-6156/81/0171-0051$05.00/0 © 1981 American Chemical Society In Phosphorus Chemistry; Quin, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
52
PHOSPHORUS CHEMISTRY
We have shown that the ylids 3 react with a number of nucleo philes ( 3 ) . In particular 3a and 3b react quantitatively with the alkylidene phosphoranes 5 to give 3 pyrrolines 6a and 6b as a mixture of diastereoisomers. The cyclisation occurs via an intra molecular Wittig reaction on the carbonyl of an ester group (4). In the same conditions, 2c reacts with 5 to give quantitatively the pyrrolines 7c (two diastereoisomers) as a result of a Wittig reaction on the carbonyl of the keto group in 3c. Downloaded by OHIO STATE UNIV LIBRARIES on October 14, 2014 | http://pubs.acs.org Publication Date: November 11, 1981 | doi: 10.1021/bk-1981-0171.ch010
_
However, the reactivity of 3-ketophosphoranes 8 with R'=Ph or Me is different from the alkylidene phosphoranes 5 owing to the double bond character of the bond due to an important contribution of the mesomeric structure 8'. As a consequence,
certain 1,3 dipoles (azides, nitrile imines, nitrile oxydes, nitrones) add either to the P=C or C=C double bond (5). We have shown that the azomethine ylids 3a and 3c add to the pseudo dou ble bond of the β-ketophosphoranes 8, R' = Ph, R' = Me. This process may be competitive with the nucleophilic addition. This is outlined in the following scheme.
In Phosphorus Chemistry; Quin, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
In Phosphorus Chemistry; Quin, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
la
2
R
1
= Ph
Ph P~CHC0R -
!
R
Q
f
(B)
i
1
addition
= Me
nucleophilic
3
»Ph P—CH— C — R
3
1
2
Ph
Ph
3
2
C ( COpMe ) * ZCH.W.C ( C O ^ e )
: Z=Ph, l b : Z=C0 Me
ZCH
cycloaddition
a
2
CH N
I Ph
C—R
°0 1
N
I Ph
2
1
2
Ph
N
2
6
R'C—C: :C—OMe * I ZCH^ ^CHC0 Me
I Ph
Ph P—CH COR zt^ 3(C0 Me) 3
3
ZCH^ ^C(C0 Me)
Q
Ph P®
©
N
I -CH
%h.
ZCH^ ^C(C0 Me)
R — C~
f
I
o
2
2
2
3
-Ph P0
5
o
-Ph P0
3
> N
:CH 2
®
2
f
N
I Ph
II
2
o
^CHC0 Me
C—-OMe
O
10
^C(C0 Me) I Ph
v N
:C—R
9
I R'C—C "C —OMe M ι - O ZCH^ ^CHC0 Me I Ph
Ph P 3
Q
3
Ph P II R'C — C O ZCH
ZCH
HC:
I Ph
ZCH^ ^C(C0 Me)
R'—C:
Downloaded by OHIO STATE UNIV LIBRARIES on October 14, 2014 | http://pubs.acs.org Publication Date: November 11, 1981 | doi: 10.1021/bk-1981-0171.ch010
2
2
54
PHOSPHORUS CHEMISTRY
Three r o u t e s a ^ , a^ and Β a r e o b s e r v e d l e a d i n g t o t h e 3 ~ p y r r o l i n e s 9, 10 a n d 6 r e s p e c t i v e l y . The r e a c t i o n o f f u n c t i o n a l i z e d i m i n i u m s a l t s 4 d e r i v e d f r o m aziridines with trimethylphosphite g i v e s a m i n o p h o s p h o n a t e s 11 by a M i c h a e l i s - A r b u z o v r e a r r a n g e m e n t . T h i s r e a c t i o n i s g e n e r a l ( 6 ) . 0
ο II
(MeO) P=0 2
II
HA
P(0Me)3
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J = N - C H , A"
With t h o s e d e r i v e d from ^ - o x a z o l i n e s and o r t h o a m i n o p h e n o l s , d e p e n d i n g on t h e r e a c t i o n c o n d i t i o n s , l i n e a r o r c y c l i c aminophosp h o n a t e s o f t y p e 11 o r 12 a r e o b t a i n e d . . (MeO) P~0 P(0Me)_ | 1» PhCH 9
A
HA PhCH=N-CH I \ Ph
PhCH
I
,A
2
0 II _ CR C T (
Ph
Ph
11 ( and) o r 0 R
0
MeOP-^ ^ υ 1 li P h C H ^ C ^ Ph
(Méo)i
H 0
and (or
,ΑΘ
12
MeO
P(OMe).
11
12
References 1. Vaultier, M. ; Carrié, R. Tetrahedron, 1979, 35, 1357. 2. Vaultier, M. ; Mullick, G. ; Carrié, R. Can.J.Chem., 1979, 57, 2876.
3. Vaultier, M. ; Danion-Bougot, R. ; Danion, D. ; Hamelin, J . and Carrié, R. J . Org. Chem., 1975, 40, 2990.
4. Vaultier, M. ; Danion-Bougot, R ; Danion, D., Hamelin, J . and Carrié, R. Bull. Soc. Chim., 1976, 1537. 5. Bestmann, H.J. and Kunstmann, R. Chem.Ber., 1969, 102, 1816. Huisgen, R. and Wulff, J . Chem.Ber., 1969, 102, 1841. Ykman, P.; L'Abbé, G. and Smets, G. Tetrahedron, 1973, 29, 195. 6. Vaultier, M. ; Ouali, M.S. and Carrié, R. Bull.Soc.Chim., II, 1980, RECEIVED
633.
July 7, 1981.
In Phosphorus Chemistry; Quin, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
