Asymmetric synthesis of (+)-phosphinothricin and (+)-2-amino-4-phosphonobutyric acid

Tetrahedron Letters,Vol.25,No.ll,pp Printed in Great Britain

ASYMMETRIC and

Research

Morooka,

Summary:

Asymmetric

butyric

acid,

of chiral

Phosphorus active

derivative strong

analogues

with

Hirayama

of

has been

to vinyl

of glutamic

Thus,

Seika

Fukatsu

Kaisha

Ltd.,

222, Japan

(+)-phosphinothricin,

enantiomers bases

ACID

and Shunzo

Meiji

Yokohama

Kohoku-ku,

(+)-2-amino-4-phosphono-

achieved

phosphorus

by the Michael

addition

compounds.

acid are interesting

(+)-phosphinothricin

((S)-(+)-l)

as biologically and its alanylalanine

(2), produced by two strains of Streptomyces, 1) have activity. 2) (+)-2-Amino-4-phosphonobutyric acid ((S)-(+)-A)

glutamate

an antiviral

for receptors activity. 3)

We have

recently

reported

the Michael

addition

of glycine

extention

(+)-PHOSPHINOTHRICIN

(bialaphos)

herbicidal

competes have

Schiff

substances.

OF

Laboratories,

synthesis

and their

glycine

SYNTHESIS

oo40-4039/84 $3.00 + -00 01984 Pergamon Press Ltd.

(+)-2-AMINO-4-PHOSPHONOBUTYRIC Minowa, * Masao

Nobuto Central

1147-1150,1984

of the preceding

in nerve

a practical Schiff

study,

cells,

synthesis

base

and has been

reported

to

of

(+)-phosphinothricin by 4) As an (4a). an effective asymmetric synthe-

to vinylphosphinate

we now report

sis of 1 and -3. According to this method, both of the S- and R-enantiomers can be prepared by the asymmetric Michael addition of chiral Schiff bases (S)5) to vinyl with

phosphorus chiral

chiral

Scheme

compounds

4a and 4b. Although a number of asymmetric reactions _. has been reported,b) there have been a few examples using 7) donors .

acceptors

Michael

1

R1 0 '&CH=CH~ R2'

4a: R1=Me, R2=Me0 , 9 4b: RI=R'=EtO -

NCH2COOEt

+

(-)-5:

(lS,2S,5S)

1147

(S)-(+)-1:

Rt=M;,

R2=OH

(S)-(+)-3:

R-=R-=OH

1148

Table

1.

Asymmetric

Michael

Addition

Additive

donor

1

4a -

(-,-I

2

4a 4a -

(+)-2 ;

4a 4b -

(-)-!j 18-crown-6d)

L

c-,-s

3

5 6

(+I-?

7 8

CH2=CHCOOMe

(+I-5

(-)-S

reactions

c 1.0 in H20.

were

was

3. g) Based

tical

purity

vinyl

(S) [851

-12.4b)

73c)

(R) [881

,":

+7.6b)

45')

(S) [481

51

+6.8b)

4oc)

(S) [431

-3 -3

68

+14.6e)

5of)

(S) [541

65

-13,oe)

45f)

(RI [541

-7 1

57

-17.7e)

56g)

(RI t6ll

55

+14.9e)

47')

(S) [581

e) c 1.0 in 6N-HCl. of

Michael

addition

was

solution

was

the residue propylene sulting

oxide solution

to give

Treatment Schiff

base

acid was

for 24 hr.

dissolved was was

under

in

for the op-

After

yellow

and purified

The results

C-)-S, obtained

') afforded

the desired acid

and the

and the solution,

amount

for 1 hr. resin

in Table

(4a) and vinylphosphonate by the condensation of glycine

(+1-l) and (+)-2-amino-4-phosphonobutyric high optical purities (entries 1 and 5).

acid

by ion-exchange

are summarized

of vinylphosphinate

25, 5S)-2-hydroxypinan-3-one,

solution

excess

at 25OC

of

The re-

(Dowex

1.

(4b) with the chiral ethyl ester and (lS,

(+)-phosphinothricin

c(S)-(+I-?),

On the other

of

for 1 hr at

of the resulting

stirred

The

of a solution

(1:l) and a large was

1.

t-butoxide of the chiral

stirred

6N hydrochloric

concentration

The solution

acid.

a solution

argon.

added

in Scheme

of potassium

by addition

to the resulting was

After

concentrated

added

followed

in ethanol-water

added.

the amino

[a]D +29'(6N-HCl)

as shown

solution

(THF) was

added

To the residue

refluxed was

on

acid. h) Corrected

undertaken

To a stirred

(2.0 eq) in tetrahydrofuran

was removed.

of t-BuOK. b) equivalents

8. d) Five

see: ref. 9.

is as follows.

1N hydrochloric

two equivalents in ref.

f) Based

(+)-glutamic

5 (1.0 eq) in THF at -78'C, compound (1.0 eq) in THF at -78V

solvent

using

1.0 , H20)

base

-78'C,

50X2)

79C’

out at -78'C

[al, +31.4"

a) (5) -

Bases

Optical purity (%),) (Confign.) ,[Calcd.l

[ali5,deg.

66

[al, 23 +17O(c

of the ketol,

procedure

(t-BuOK) Schiff

on

used.

on

The asymmetric general

carried

c) Based

of the additive ref.

HMPAd)

Schiff

+13.4b)

1 -

c-,-s

4b CH2=CHCOOMe

a) All

Glycine

acid-,

Compd. Total no. yield(%)

acceptor

4

Chiral

/-Amino

/-MichaelEntry

using

hand,

respectively, the reactions

t(S)in of

4a and 4b with the other chiral Schiff base (+)-I, similarly prepared from (lR, 9) gave their enantiomers, 2R, 5R)-2-hydroxypinan-3-one, (-)-phosphinothricin (CR)-(-j-l) in high

from which sources,

and

optical

(-)-2-amino-4-phosphonobutyric purities

the chiral

the present

(-)-isomers

(entries

ketols method

2 and 6).

are prepared, has

of 1 and 2 in high

advantage optical

acid Since

((R)-(-)-3), both

are readily in providing

purities.

respectively,

enantiomers available both

of a-pinene,

from natural

(S)-(+)-

and

CR)-

1149

In order phorus

to clarify

the high

the following

compounds,

chiral

induction

studies

were

observed

carried

for the vinyl

out.

Addition

of

phos-

(-1-5

to 4a in the presence of hexamethylphosphoric triamide (HMPA) or dicyclohexyl10) gave 18-crown-6 (18-crown-61, which has strong ability to solvate cations, lower

optical

purity

may be explained

of the product

(S)-(+)-l

(entries

These

3 and 4).

results

intermediate as shown in Fig. 11) and Koga et al. 12) 1, which is similar to those proposed by Meyers et al. --It is assumed that the coordination of the electron pairs on the nitrogen atom and the oxygen plays

ment

by the existence

atom of phosphoryl

a central of

role

C-)-S and

(-)-I) and the

7 and 8). course

(+)-2 with

(+)-isomer

That

studies

methyl

yields

of potassium

(5) gave

alkoxide

Interestingly,

addition.

acrylate

t(S)-(+)-I),

(-)-glutamic

treat-

acid

((R)-

re-

(entries

of 2 to methyl

the same as that of alkylation

of 2 and opposite to vinyl

to the potassium

orientated

is, the stereochemical

of the addition

late was

group

in this highly

in good optical

spectively,

of the chelate

'0

acry5)

‘!

to that of the addition

phosphorus

compounds.

on the detailed

4

6 11

Further

mechanism

?v0;

&

*P

Fig.1

are now

/ ‘R2

R’

in progress. The herbicidal (*)-l_ and

activity

(R)-(-)-l

and Professor

of Tokyo,

for their

valuable

References

(S)-(+1-l_ was

advice

remarkably

stronger

than those of

treatment.

We are grateful

Acknowledgment: versity

of

in foliage

to Professor

Kikumasa

throughout

Sato,

Teruaki

Yokohama

Mukaiyama,

National

The Uni-

University,

this work.

and Notes --

1) E. Bayel,

K. H. Gugel,

and H. Zahner, Ogawa,

Helv.

T. Turuoka,

Yoshida,

K. Hagele,

Chim.

Acta,

H. Watanabe,

S. Inouye,

H. Hagenmaier, E,

224

K. Totsukawa,

and T. Niida,

S. Jessipow,

(1972);

Y. Kondo,

T. Suzuki,

Sci. Reports

of Meiji

W. A. Ke)nich, T. Shomura,

C. Moriyama, Seika

Y.

J.

Kaisha,

1973,

34. 2)

K. Tachibana,

T. Watanabe,

Seika

1980,

Kaisha,

Felcht,

Angew.

3) S. G. Cull-Candy, 1976,

408;

4) N. Minowa, 24,

2391

and Y. Sekizawa,

K. Weissermel,

Int. Ed. Engl.,

J. F. Donnellan,

J. F. Koerner S. Fukatsu,

H. J. Kleiner,

20,

223

M. Takada,

Reports

M. Finke,

of Meiji

and U. H.

(1981).

R. W. James,

and C. W. Cotman,

T. Niida,

Sci.

and G. G. Lunt,

Brain

Research,

and K. Sato,

216,

Nature, 192

Tetrahedron

(1981). Lett.,

(1983).

5) S. Yamada, T. Oguri, (1978);

27;

Chem.

Y. Suzuki,

T. Oguri, N. Kawai,

and T. Shioiri, T. Shioiri,

J. A. Bajgrowicz,

Viallefont,

Tetrahedron

J. Chem.

B. Cossec,

Lett.,

Sot. Chem.

and S. Yamada,

24,

Chem.

Ch. Pigiere,

3721

(1983).

Comm.,

Pharm.

1976,

Bull.,

R. Jacquier,

136;

2,

and Ph.

803

1150

6) A. I. Meyers,

and C. E. Whitten,

Hashimoto,

S. Yamada,

Hashimoto,

N. Komeshima,

T. Mukaiyama,

and K. Koga,

T. Takeda,

S. Inoue,

and K. Ogura, K. Miura,

T. Hoshiko,

and M. Hulce,

Tetrahedron

and C. Ullenius,

8) Y. Ogawa,

T. Tsuruoka,

Kaisha,

42.

1913,

9) According

2.64,

(neat) and the

10) HMPA:

were

Chem.

Lett.,

1981,

797.

Lett., 1978,

11) A. I. Meyers, 567

estimated

(1976).

Tetrahedron

[ali

R. H. Mueller,

Crown

Sci. Reports

[J. Org.

-37.O"(c from

92.5%

G. W. Gokel,

1976,

653;

T. Mukaiyama,

461;

T. Takeda,

K. Kamata,

M.

Chem.,

36,

2.60, CHC13)

of the

and 82.59,

Y. Hirako,

[lit.5)

[a], 22 +47.1° from

(S)- and

respectively.5)

J. Am. Chem.

Sot.,

and N. W. Rebert,

and T. Takeda,

and T. Mukaiyama,

and M. E. Ford,

Seika

2319

was obtained

H. M. Gerdes,

T. Hoshiko,

of Meiji

(+)-c-pinene,

and A. K. Willard,

ether:

G. Knaus,

M. Iijima,

(1982).

was prepared

to be at least

T. Takeda,

H. Malmberg,

(R)-isomer, [ali +33.0°(c 2.60, CHC13), 22 -42.0°(neat). The optical purities

R. E. Ireland,

98, 2868

3823

J. P.

(1981). 461;

K. Yamamoto,

(1982) ;

T.

S. Mitamura,

53, 2307

[a],

(-)-a-pinene, (R)-ketols

CHC13)],

797;

3711

and Pierce

(S)-2-hydroxypinan-3-one,

-38.9“(c

[ali

1981,

S.

(1979);

1165;

1978,

S.

(1979);

2437

G. Posner,

Lett.,

and T. Niida,

of Carlson

21,

1977,

323;

Chem.,

Chem.

2,

23,

S. Inouye,

to the method

(1971) 1,

ibid.,

1973,

(1975);

z_Z, 771

G. Tsuchihashi,

Pure Appl.

ibid.,

ibid.,

Lett.,

Lett.,

Lett.,

Bull.,

913;

and T. Takeda,

and T. Mukaiyama,

Pharm.

6266

Chem.

1981,

Tetrahedron

Y. Hirako,

and Y. Ogimura, Nilsson,

ibid.,

97,

Sot.,

and K. Koga,

and M. Osaki,

and N. Iwasawa,

Mallamo,

Chem.

S. Yamada,

Mukaiyama

7) T. Mukaiyama,

J. Am. Chem.

J. Am. Chem.

ibid.,

Sot.,

98,

(1976).

12) S. Hashimoto K. Koga, (Received

and K. Koga,

Chem.

Pharm.

in Japan

Tetrahedron

Bull.,

10 December

27,

2760

1983)

Lett., (1979).

1978,

573;

S. Hashimoto

and