Unusual conversion of sugar-oximes to sugar-nitriles with ruthenium catalysts

Article abstract of DOI:10.1081/SCC-120014784

Unusual conversion of Sugar-oximes to sugar-nitriles in the presence of ruthenium catalysts such as Cl₂(PCy₃)₂Ru=CHPh, Cl₂Ru(PPh₃) and RuCl₃ in benzene at 60°C was reported.

Full text of DOI:10.1081/SCC-120014784

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UNUSUAL CONVERSION OF SUGAR-OXIMES TO SUGAR-
NITRILES WITH RUTHENIUM CATALYSTS
Arindam Talukdar a
a Organic Chemistry Technology Division , National Chemical Laboratory , Pune,
Maharashtra, 411 008, India
Published online: 22 May 2009.
To cite this article: Arindam Talukdar (2002) UNUSUAL CONVERSION OF SUGAR-OXIMES TO SUGAR-NITRILES WITH RUTHENIUM
CATALYSTS, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
32:22, 3503-3508, DOI: 10.1081/SCC-120014784
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 22, pp. 3503–3508, 2002
UNUSUAL CONVERSION OF
SUGAR-OXIMES TO SUGAR-NITRILES
WITH RUTHENIUM CATALYSTS
Arindam Talukdar
Organic Chemistry Technology Division,
National Chemical Laboratory, Pune-411 008, Maharashtra, India
E-mail: arindamt@dalton.ncl.res.in
ABSTRACT
Unusual conversion of Sugar-oximes to sugar-nitriles in the
presence of ruthenium catalysts such as Cl2(PCy3)2Ru¼CHPh,
Cl2Ru(PPh3) and RuCl3 in benzene at 60ꢀC was reported.
Key Words: Sugar-oxime; Sugar-nitrile; Ruthenium catalyst
Synthesis of novel heterocyclic derivatives fused to sugar backbone is
of current interest.[1] We have identified[2] ring closing metathesis (RCM)
reaction[3] as a tool to fabricate some novel heterocyclic molecules. Synthesis
of cyclic molecules of the type 2 from sugar dienes (1) by using RCM
method was undertaken (Sch. 1) in the present work. Preparation of 1
was accomplished from 3-O-allyl-1,2 : 5,6-di-O-isopropylidine-a-D-gluco-
furanose[4] (3) in 4 steps (Sch. 2).
Treatment of 1 with 3 mol % of Grubbs’ catalyst Cl2(PCy3)2Ru¼ CHPh
in benzene at 60ꢀC gave a single major product whose structure was not in
conformity with expected product (2). Based on spectral data and elemental
3503
DOI: 10.1081/SCC-120014784
Copyright & 2002 by Marcel Dekker, Inc.
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3504
TALUKDAR
Scheme 1.
(a) 0.8% H2SO4, MeOH, rt, 85%; (b) NaIO4, CH2Cl2, rt, 80%; (c) NH2OH,
pyridine, EtOH, rt, 82%; (d) Ag2O, Allyl bromide (neat), reflux, 76%.
Scheme 2.
analysis, structure (5) was proposed for the new product. For example, in the
1H-NMR spectrum of 5, the resonances due to H-4 was observed at 4.81 ppm
as a doublet (J3,4 ¼ 3.5 Hz). Rest of the spectral data was in conformity with 5.
The 13C-NMR (ꢀCꢁN ¼ 115.5 ppm) and IR (gCꢁN ¼ 2360 cmÀ1, weak) spectra
of 5 also supported the assigned structure (Sch. 3).
The cyanide functionality is useful in many chemical transformations.
Although several methods are reported for its preparation, conversion of
oxime to nitrile using a dehydrating reagent is a widely used methodology.
The scanty reports on the synthesis of sugar substituted nitriles may be
attributed to the use of acidic reagents in the existing methods, which
cleave acid labile isopropylidene groups leading to a mixture of products.
The method reported herein involves mild conditions and hence the acid
labile groups are tolerated.
In order to probe the unexpected nitrile formation,[5] we performed
several experiments to address some critical issues. For instance, unpro-
tected oxime (6) also underwent transformation with catalytic amount
of Cl2(PCy3)2Ru¼CHPh to obtain the same nitrile derivative (5), thus,
indicating that protecting groups are not needed (Table 1). The 3-oxime
derivative (7) as well as acetophenone oxime (8), without the a-hydrogen,
were inert to the treatment of Cl2(PCy3)2Ru¼CHPh in benzene at 60ꢀC,
suggesting the essentiality of a-proton. Conversion of 1 and 6 into 5 also
occurred with 3 mol % of Cl2Ru(PPh3) in benzene at 60ꢀC. However, with
3 mol % of RuCl3, transformation of 1 ! 5 was sluggish. With addition of

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CONVERSION OF SUGAR-OXIMES TO SUGAR-NITRILES
3505
Scheme 3.
increased quantity of RuCl3 (10 mol %), complete conversion was observed
in refluxing benzene after 16 h. With PPh3 alone in refluxing benzene, com-
pound 1 and 6 were recovered unchanged. The versatility of this method was
evident by several examples shown in Table 1.
In conclusion, we have developed a new method of conversion of
sugar-oximes into sugar-nitriles with Grubbs’ catalyst as well as other
ruthenium salts. The reaction is high yielding, with easy workup procedure
and involves mild conditions, which enables acid labile isopropylidene
groups to remain intact. This method is also applicable to aryl-oxime as
depicted in Entry 9 (Table 1).
EXPERIMENTAL
For column chromatography, silica gel (60–120 mesh) and light
petroleum ether (b.p. 60–90ꢀC) was used. IR spectra were recorded on a
1
Perkin-Elmer 16 PC-FT IR spectrometer. H-NMR and 13C-NMR spectra
were taken on a Bruker AC-200 spectrometer. Elemental analysis was
performed on Carbo-Elba elemental analyzer. The protected and the
unprotected oximes were prepared on line with Sch. 2.
General Procedure
0.5 g of oxime (2.05 mmol) in 10 mL dry benzene was taken in a 25 mL
R.B. flask equipped with a spin bar, reflux condenser and nitrogen inlet.
Ruthenium salts 3 mol % of Cl2(PCy3)2Ru¼CHPh/Cl2Ru(PPh3) or

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TALUKDAR
Table 1. Conversion of Aldoximes to Nitriles
Yield
(%)c
Entry
1
Oxime
Reagenta
Time in hb
10.5
Nitrile
N
N
O
Cl2(PCy3)2Ru¼CHPh
81
O
O
H
H
O
O
O
O
O
O
H
H
H
H
N
N
2
Cl2(PCy3)2Ru¼CHPh
(PPh3)3RuCl2
RuCl3
10
10
16
85
81
81
O
O
HO
O
O
O
O
O
O
H
H
H
H
O
3
4
Cl2(PCy3)2Ru¼CHPh
24
No product
—
O
O
HO
N
N
N
O
Cl2(PCy3)2Ru¼CHPh
(PPh3)3RuCl2
RuCl3
6
6.5
15
88
83
80
O
O
HO
O
O
MeO
O
MeO
O
N
N
O
5
6
Cl2(PCy3)2Ru¼CHPh
Cl2(PCy3)2Ru¼CHPh
9
78
HO
O
O
BnO
O
BnO
O
O
10
90
N
O
N
O
O
HO
O
N
O
O
O
N
OH
O
7
8
9
Cl2(PCy3)2Ru¼CHPh
8
76
O
BnO
BnO
BnO
BnO
BnO
OMe
BnO
N
OMe
N
OH
O
Cl2(PCy3)2Ru¼CHPh
(PPh3)RuCl2
RuCl3
9
9
16
79
76
70
O
BnO
BnO
BnO
BnO
BnO
BnO
OMe
H
OMe
Cl2(PCy3)2Ru¼CHPh
12
75
MeO
N
MeO
N
OH
aCl2(PCy3)2Ru¼CHPh (3 mol %), (PPh3)RuCl2 (3 mol %), RuCl3 (10 mol %);
bReaction were carried out in benzene at 60ꢀC; Isolated.
c

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CONVERSION OF SUGAR-OXIMES TO SUGAR-NITRILES
3507
10 mol % of RuCl3 was added. The reaction mixture was heated at 60ꢀC for
9–16 h. Solvent was removed under reduced pressure and the residue
purified on silica gel to give respective nitrile products.
Spectral data of some selected compounds are given below:
1
Entry 2: H-NMR (200 MHz, CDCl3): ꢀ 1.24, 1.40 (2s, 6H), 4.12 (d,
1H, J ¼ 3.5 Hz), 4.25 (m, 2H), 4.54 (d, 1H, J ¼ 3.5 Hz), 4.81 (d, 1H,
J ¼ 3.5 Hz), 5.2–5.46 (m, 2H), 5.90 (m, 1H), 5.94 (d, 1H, J ¼ 3.5 Hz);
13C-NMR (50 MHz, CDCl3): ꢀ 26.4, 27.6, 70.2, 82.3, 82.9, 105.9, 113.6,
115.5, 119.3, 134.0; IR: gCꢁN 2360 cmÀ1 (weak); Anal. calcd. for C11H15NO4:
C, 58.6; H, 6.6; N, 6.2. Found: C, 58.5; H, 6.8; N, 6.2.
Entry 5: 1H-NMR (200 MHz, CDCl3): ꢀ 1.23 (s, 3H), 1.38 (s, 3H), 4.15
(d, 1H, J ¼ 3.1 Hz), 4.58 (d, 1H, J ¼ 3.1 Hz), 4.77 (s, 2H), 4.86 (d, 1H,
J ¼ 3.1 Hz), 6.00 (d, 1H, J ¼ 3.1 Hz), 7.3 (m, 5H); 13C-NMR (50 MHz,
CDCl3): ꢀ 25.9, 27.2, 69.2, 72.6, 81.9, 105.2, 112.4, 114.1, 127.6, 128.0,
128.4. IR: gCꢁN 2250 cmÀ1 (weak). Anal. calcd. for C15H17NO4: C, 65.45;
H, 6.18; N, 5.09. Found: C, 65.60; H, 6.36; N, 5.05.
Entry 6: 1H-NMR (200 MHz, CDCl3): ꢀ 1.29, 1.38 (2s, 6H), 4.00
(dd, 1H, J ¼ 5.9, 11.7 Hz) 4.29 (dd, 1H, J ¼ 4.4, 11.7 Hz), 4.76 (m, 2H), 5.0–
5.5 (m, 4H), 5.94 (m, 1H); 13C-NMR (50 MHz, CDCl3): ꢀ 24.9, 26.0, 67.6, 70.9,
82.3, 83.4, 106.9, 113.4, 115.6, 117.2, 132.5; IR: gCꢁN 2295 cmÀ1 (weak); Anal.
calcd. for C11H15NO4: C, 58.6; H, 6.6; N, 6.2. Found: C, 58.8; H, 6.7; N, 6.2.
Entry 8: 1H-NMR (200 MHz, CDCl3): ꢀ 2.52 (dd, 1H, J ¼ 7.7,
12.9 Hz), 2.96 (dd, 1H, J ¼ 5.8, 12.9 Hz), 3.42 (s, 3H), 3.93 (t, 1H,
J ¼ 9.6 Hz), 4.12 (d, 1H, J ¼ 9.6 Hz), 4.51 (d, 1H, J ¼ 9.6 Hz), 4.61 (d, 1H,
J ¼ 12.9 Hz), 4.84 (m, 6H), 5.22 (m, 2H), 6.1 (m, 1H), 7.32 (m, 15H);
13C-NMR (50 MHz, CDCl3): ꢀ 35.7, 56.3, 62.6, 65.4, 75.1, 75.7, 79.1, 79.6,
81.4, 102.0, 117.4, 118.5, 126.7–128.2, 132.8, 136.8, 138.0, 138.5; IR: gCꢁN
2335 cmÀ1 (weak); Anal. calcd. for C31H33NO5: C, 74.5; H, 6.6; N, 2.8.
Found: C, 74.3; H, 6.7; N, 2.9.
ACKNOWLEDGMENT
The author is grateful to Dr. M. K. Gurjar for fruitful suggestions and
CSIR, New Delhi, for the financial support in the form of Senior Research
Fellowship.
REFERENCES
1. For recent reviews on carbohydrate chemistry, see Chem. Rev. 2000,
100, 4265–4712.

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3508
TALUKDAR
2. Gurjar, M.K.; Murugaiah, A.M.S.; Cherian, J.; Chorghade, M.S.
Carbohydr. Lett. 1999, 3, 343–348; Gurjar, M.K.; Krishna, L.M.;
Reddy, B.S.; Chorghade, M.S. Synthesis 2000, 557–560; Gurjar,
M.K.; Ravindranadh, S.V.; Karmakar, S. J. Chem. Soc., Chem. Comm.
2001, 241–242.
3. Nguyen, S.T.; Johnson, L.K.; Grubbs, R.H.; Ziller, J.W. J. Am. Chem.
Soc. 1992, 114, 3974–3975; Roy, R.; Das, S.K. J. Chem. Soc., Chem.
Commun. 2000, 519–529; Pandit, U.K.; Overkleeft, H.S.; Borer, B.C.;
Bieraugel, H. Eur. J. Org. Chem. 1999, 5, 959–968; Grubbs, R.H.;
Chang, S. Tetrahedron 1998, 54, 4413–4450; Furstner, A. Angew.
Chem. Int. Ed. Engl. 2000, 38, 3012–3043.
4. Yong-Li, Z.; Tony, K.M.S. J. Org. Chem. 1997, 62, 2622–2624;
Buehler, E. J. Org. Chem. 1967, 32, 261–265.
5. Friedrich, K. In The Chemistry of Triple-Bonded Functional Group,
Part 2; Patai, S., Rappoport, Z., Eds.; John Wiley and Sons Ltd.,
1983; 1345–1376; Brink, A.J.; De Villiers, O.G.; Jordan, A.S. Afr. J.
Chem. 1978, 31, 59–65.
6. Crossby, J.; Moiller, J.; Parratt, J.S.; Turner, N.J. J. Chem. Soc., Perkin
Trans. 1 1994, 1679; Luo, F.-T.; Jeevanandam, A. Tetrahedron Lett.
1998, 39, 9455.
Received in the UK July 19, 2001