Synthesis of C- α-D-glucosyl-α-amino acids

Tetrahedron: Asymmetry Vol. 4, No. 11, pp. 23432346.1993 Ritcd in Gnat Britain

Synthesis

09574166193 .%.0&.00 PergamonpnrrLtd

of

Acids

C- a-D-Glucosyl-a-amino

M K G-jar*, Indian Institute

A S hbinkar and M Syamb of Chemical Technology, Hyderabad 500 007, India

(Received in UK 15 September 1993)

Abstmct

: The Sharpless asymmetric dihydroxylation of s-allyl-U-D-glucopyranoside with variety of ligands and its application to synthesise c-a -D-glucosyla -amino acids have been described. C-Glycosylamino of their

ability

chemical

stability,

developments* very

little

they. are

that work

we believe

that

acids

to withstand

(1) arose accepted

on C-glycosylamino

acids

is a significant

In our previous

because

of the

cial

Ieve+.

communication4,

significantly

introduction

In continuation,

as shown in scheme as an ideal

allylglycoside

inhibitors’.

alternate

because

of their

In spite

andE-glycosylamino encountered

to develop

primarily

virtue

acids,

of many practically

in literature3. and versatile

high

Therefore, protocols

to-

acids (Il.

(ADH) of ally1 D-glucopyranosides has been

scope

been

years

By the

glycosidase of g-

has

in recent

of hydrolysis.

as potential

in the synthesis

there

interest

process

have occurred

wards C-glycosylamino

reaction

considerable

the biological

precursor

we described

to prepare improved

of reagents we planned

1. The proposition for the target

in terms such as

the

AD-mix-o

I, was based Scheme - 1

dihydroxyiation Since

simplicity

then

ADH5

and predictability

and AD-mix-g

at the

commer-

of c-glycosyl-

a -amino

acid

the enantiomerically

(Ill).

2343

asymmetric

derivatives.

of efficiency,

retrosynthesis

to prepare molecule

the Sharpless

glucosylglycerol

(I)

pure diol (II), serving

on the application

of ADH on c-

M. K. GURJARet al.

2344

The

preparation

cosepentaacetate ward

of s-ally1

(1) and 7

exercise

. Subsequently,

by employing

NaH-BnBr

representative

examples

2,3,4,6-tetra-g-acetyl-cc-D-glucopyranoside

allyltrimethylsilane

in the

2 was deacetylated

combination

in dry

of the present

presence

under DMF to

ADH study Scheme

Zemplen provide

(scheme

(2) from

of BF3:OEt2 condition

2).

- 2

MO BnO

0

’

C

(b)

(i)

NaOMe,

Treatment merit

MeOH,

mixture

into

the

The

HPLC

Py,

of 3 with of dials

mono

TBS-ether

analysis

RT,

(lrl),

70”,

3h,

2h, 96%; L&and,

O”-RT,

DMF,

NaH,

ISh,

70-85%;

in I:1 t-BuOH-H20

In order

(6/7) or the

of 6/7

(ii)

BnBr,

R=H R=TBS R=fr

Oo-RT,

d) TBS-Cl,

ISh,

92%; (c)

Imid.,

CH2C12,

to determine

the

mono trityl-ethers

on a chiral

column

(chira-ccl

at O”-RT for ratio,

4/5

18 h gave

a diastereo-

were

converted

selectively

(S/9) by adopting

standard

procedures.

OD,

8% isopropanol/n-?exane,

Table

Entry

Substrate

Ligand

Product 2R

Yield

I

3

AD-mix-

61

39

73%

3

DHQD-9-0phenathryl ether

78

22

83%

3

3

DHQD-p-CIbenzoate

64

36

84%

4

3

DHQ-9-Ophenanthryl

41

59

75%

ether

DHQD-J-Ophenanthryl

70

30

70%

ether

2

8

2s

2

5

OR

90%.

AD-mix-B

(B/5).

dLl

2

R=fr

K3Fe(CN)6,tBuOH-H20

RT, )h; 75%; e) TrCI,

c

R = TBS

1

c x

R=H

l dLk

Ref.6,

OH 7

+

-

h

OsOp

cell

OAc

I

a)

benzylated

2 and 3 formed

-F

C

D-glu-

a straightfor-

and then

3. Compounds

b L

was

UV

C-a-D-Glucosyl-a-amino

228 nm) resolved Since

the

other

cinchona

Indeed

the

mixture

diastereofacialselectivity alkaloids,

ADH reaction

tion of TBS-ethers On the

other

expected,

the

(6/7) showed with

reverse

by

and multigram separated

instance,

derivative,

the

oxidation

and

10% Pd-C at

formed

36 h, followed

for

acid derivative

a) (i) Py,

the hope to improve ether

with

gel column

esterification I atm

into

reaction

was

the

ADH

to utilise

StereOSekCtiVitY8.

by derivatisa-

78:22 as judged by HPLC.

4) as ligand,

ratio

1, Table).

we decided

2) followed

in the ratio,

3 demonstrated,

41:59 for 6/7.

the diastereomeric

Both these

converted

group

(entry

(entry

~-o-glucosyla-amino

trityl

of 61:39 (6/7) (entry

Other

as

exmaples

in the Table.

scale,

displacement

ratio

improvement

by silica

8 was first

of 10 over &amino

significant

diastereofacialselectivity

to nucleophilic

Jones

with

DHQ-9-0-phenanthrylether

into the corresponding For

azido

ligands,

pure (2R)-8 and (2S)-9 isomers.

subjected

the

was only moderate,

AD-mix-6

with 2 and 3 are included

(8/9) were cleanly

dently

with

as chiral

On a preparative merically

to provide

of 3 with DHQD-9-g-phenanthryl

hand,

of ADH reactions tives

efficiently

2345

acids

removed providing

in methanol

by conventional

mixture

of trityl

chromatography, products

ether

deriva-

thus providing

enantio-

transformed

indepen-

were then

acid derivatives. the with

mesyl

by using the

containing acetylation

derivative

with

NaN3-DIMF at

80% aqueous

azido

ester

acetic

(IO).

1.2 equivalent with

MsCl-Py

120“. From

Ac20-Py

and then

the

resulting

acid

followed

Exhaustive

of Boc20 to give

reduction

was then pero-c-glucosyl-

(11)9.

MsCI, CH2C12, O”-RT, 3h; (ii) NaN3, DMF, 120”, 3h, 35% (from 81, (iii) 80% AcOH,

SO”, 2h, 70%; (iv) Jones reagent, (b) (i) Pd-C,

EtOH, BOC20,

In a similar (13) -via the

azido

Oa-RT,

Ih; (v) CH2N2,

H2 (1 atm), 36 h, 7096; (ii) Ac20-Py,

fashion, ester

MeCOMe,

compound

substrate

9 was

also

12, by following

converted essentially

EtOEt,

O”, 30 min, 63%,

O”-RT, ISh, 90%. into

the s-glycosylamino

identical

reaction

acid

conditions.

M.K. GUIUAR~~ al.

2346

In the

preceding

g-glycosylamino

acids.

acids

upon the g-alkenylglycosides

depending

lines,

we have

The process

described

a simple

in principle

could

used

and versatile

be expanded

as substrates.

approach to other

This study

to synthesise

C_glycosylamino is under

progress.

Adawwledgments We acknowledge References 1.

UGC, New Delhi for Junior

Wittman,

V.;

July 5-10,

1992, pp 268.

Kunz,

3.

a)

4.

Gurjar,

5.

a) Sharpless,

Kessler,

H.;

K.B.;

H.-L.;

V.;

Horton,

8.

a) Jacobsen,

Morikawa,

D.; Miyaki, E.N.;

1988,

Lubben,

110,

D.;

3.;

for

Wang,

from

4.34

Lett.

= 6.75

Hz);

b) Ogino,

2H), 4.92 (t,

[a],

12.5 Hz),

+36 4.23 (m,

8.5 Hz); [o]D +42

IICT Communication

Paris-France,

Z.-M.;

Res.

Crispino,

G.A.;

Hartung,

X-L.;

J.

J.; Jeong,

K-S.;

Chem.

1992,

Org.

1992, 48, 10515.

Co. Inc.

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Tetmhedmn

lH,

H.; Lett.

K.B. J. Am. Chem.

G.; Sharpless,

Manoury,

E.; Shibata,

1991,

5761;

(c 1.0, 2H),

lH,

6

J = 2.2,

41,

T.;

c) Oi,

Beller,

R.;

M.;

Sharpless,

1.40 (s, 9H), 2.01 (s, 6H), 2.03 (s, 3H), 13.5 Hz),

J = 9.0 HZ), 5.16 (t, CHC13);

b) Data

for

lH,

II:

‘H

4.21 (dd,

lH, J = 4.4,

J = 9.0 Hz), NMR (200

5.28 (d,

4.39 (m,

IH),

4.91

(t,

IH,

J = 8.3 Hz),

13.5 lH,

J

MHz, CDC13):

2.08 (s, 3H), 2.12 (s, 3H), 3.75 (s, 3H), 4.06 (dd,

(c 1.0, CHC13).

No. 3263

Engl.

1990, 525.

W.S.; Schroder,

Y.;

Ed.

1992, 3, 21.

Xu, D.; Xhang,

Chem.

Int.

Chem.

1992, 33, 2095.

6 1.43 (s, 9H), 2.04 (s, 6H), 2.0,

Y.L.;

13: 1H NMR (200 MHZ, CDC13):

(m,

Symposium,

M. Angew.

Asymmetry,

I.; Mungall,

K.B.,

Kottehan,

E.; Synthesis,

Aldrich

2.07 (s, 3H), 3.73 (s, 3H), 3.96 (dd, Hz),

Carbohydrate

K.B.; Tetrahedron,

T.; Carbohydr.

1968;

M.;

W.; Bennan,

Sharpless,

Marko,

Sharpless,

K.B. Tetrahedron a) Data

Kock,

Tetrahedron

Amberg,

was purchased

7.

International

G.; Purkner,

AS.

57, 2768; b) Kolb, H.C.; AD-mix+

XVIth

Wittman,

M.K.; Mainkar,

Kwong,

9.

to ASM.

award

Chem. Int. Ed. Engl. 1987, 26, 294.

H.; Angew.

Kesseler,

H.;

1992, 31, 902; b) Simchen,

Sot.

Fellowship

and Notes

2.

6.

Research

5.18 (t,

IH,

J =

IH,

J =