3,5-Dinitrobenzoic acid catalyzed synthesis of 2,3-unsaturated O- and S-glycosides and tetrahydropyranylation of alcohols and phenols

Article abstract of DOI:10.1016/j.tetlet.2014.10.093

A simple procedure for the synthesis of 2,3-unsaturated glycosides in acetonitrile and tetrahydropyranylation of alcohols and phenols in dichloromethane in the presence of 3,5-dinitrobenzoic acid is described. A variety of alcohols and thiols are reacted with glycals to give the desired products in high yields with high α-selectivity.

Full text of DOI:10.1016/j.tetlet.2014.10.093

Tetrahedron Letters 55 (2014) 6878–6881
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Tetrahedron Letters
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3,5-Dinitrobenzoic acid catalyzed synthesis of 2,3-unsaturated
O- and S-glycosides and tetrahydropyranylation of alcohols and
phenols
⇑
Naganjaneyulu Bodipati, Srinivasa Rao Palla, Venkateshwarlu Komera, Rama Krishna Peddinti
Department of Chemistry, Indian Institute of Technology, Roorkee 247 667, Uttarakhand, India
a r t i c l e i n f o
a b s t r a c t
Article history:
A simple procedure for the synthesis of 2,3-unsaturated glycosides in acetonitrile and tetrahydropyrany-
lation of alcohols and phenols in dichloromethane in the presence of 3,5-dinitrobenzoic acid is described.
A variety of alcohols and thiols are reacted with glycals to give the desired products in high yields with
Received 2 September 2014
Revised 14 October 2014
Accepted 15 October 2014
Available online 22 October 2014
high a-selectivity.
Ó 2014 Published by Elsevier Ltd.
Keywords:
3,5-Dinitrobenzoic acid
Organocatalyst
Ferrier rearrangement
O-glycosylation
S-glycosylation
2,3-Unsaturated glycopyranosides are a class of important
chiral intermediates1,2 in the synthesis of biologically active
compounds such as glycopeptide building blocks,3 oligosaccha-
rides,4 and modified carbohydrates.5a In addition 2,3-unsaturated
glycosides have also been employed in the synthesis of antibiotics,
nucleosides, and various natural products.5 Because of the impor-
tance of 2,3-unsaturated glycosides, several reports have appeared
in the literature. The synthesis of 2,3-unsaturated glycopyrano-
sides is generally achieved by the treatment of corresponding gly-
cal with an alcohol or thiol in the presence of a Lewis or a Brønsted
acid. This reaction was discovered by Ferrier by using BF3ÁEt2O as a
Lewis acid catalyst and is popularly known as the Ferrier rear-
rangement or Ferrier type I reaction.2a Apart from BF3ÁEt2O several
other Lewis acid catalysts, oxidants or protic acids such as ZnCl2,6
H3PO4,7 InCl3,8 SnCl4,9 Yb(OTf)3,10 FeCl3,11 montmorillonite K-10,12
Dy(OTf)3,13 DDQ,14 I2,15 I(Coll)2ClO4,16 CAN,17 CeCl3Á7H2O,18 HClO4/
SiO2,19 MeOHÁHCl,20 and N-iodosuccinamide21 have been reported
to affect this rearrangement. All of these methods offer several
advantages but some of them suffer drawbacks due to low yield,
longer reaction times, harsh reaction conditions, and the use of
air sensitive catalysts. Owing to the importance of the Ferrier
rearrangement products, the introduction of new and efficient
catalysts for this transformation is still in demand.
With an objective of developing a viable procedure for Ferrier
rearrangement, we focused on finding a low cost and efficient
catalyst that would give high yields and easy handling procedure
under aerobic conditions. In continuation of our work on novel
organocatalysts for organic transformations,22 we became inter-
ested to use very cheap 3,5-dinitrobenzoic acid (3,5-DNBA, <$0.1
per gram) as organocatalyst for the aforementioned reaction.
Though 3,5-DNBA has been used as an additive in many reac-
tions,23,24 it has not been used as a catalyst. In the present Letter,
we describe the successful utilization of 3,5-DNBA as an organocat-
alyst for the Ferrier rearrangement of glycals and tetrahydropyr-
anylation of various primary and secondary alcohols and phenols.
In our preliminary experiment, we allowed to stir a mixture of
benzyl alcohol (1 mmol) and glucal 1 (1.1 mmol) in the presence of
3,5-DNBA (0.2 mmol) in CH2Cl2 at room temperature for 24 h.
Under these conditions the reaction did not proceed. When we car-
ried out the reaction at 80 °C in CH3CN, the reaction underwent
smoothly to give 2,3-unsaturated-O-glucopyranoside 3e in 81%
yield. However, the reaction with low catalyst loading (0.1 mmol)
led to longer reaction times and resulted in the formation of glyco-
side 3e in low yield. Having developed conditions in hand, the
methodology was applied for alcohols such as allyl alcohol, propa-
nol, butanol, and iso-butanol. The 3,5-DNBA catalyzed reactions of
all these reactants proceeded smoothly under the same conditions
to afford the corresponding O-glycosides 3a–d in high yields
(Scheme 1, Table 1). Similarly, the Ferrier rearrangement of
⇑
Corresponding author. Tel.: +91 133 228 5438; fax: +91 133 227 3560.
E-mail addresses: rkpedfcy@iitr.ac.in, ramakpeddinti@gmail.com (R.K. Peddinti).
galactal
2 provided the 2,3-unsaturated-O-galactopyranosides
http://dx.doi.org/10.1016/j.tetlet.2014.10.093
0040-4039/Ó 2014 Published by Elsevier Ltd.

N. Bodipati et al. / Tetrahedron Letters 55 (2014) 6878–6881
6879
COOH
R1
R1
OAc
O
OAc
O
3,5-DNBA (20 mol%)
CH3CN, reflux
R2
AcO
R2
RXH
NO2
3,5-DNBA
O2N
XR
X = O, S
1: R1 = H, R2 = OAc
2: R1 = OAc, R2 = H
3: R1 = H, R2 = OAc, X = O
4: R1 = OAc, R2 = H, X = O
5: R1 = H, R2 = OAc, X = S
6: R1 = OAc, R2 = H, X = S
Scheme 1. Synthesis of 2,3-unsaturated glycopyranosides by using alcohols and thiols in the presence of organocatalyst 3,5-DNBA.
Table 1
Ferrier rearrangement of 2,3-tri-O-acetyl-D-glycals with alcohols and thiols in the presence of 3,5-DNBA
Entry
Substrate
Alcohol/thiol
Time (h)
Product
Glycoside
Yielda (%)
86
a
/bb
O
O
O
AcO
AcO
AcO
AcO
OH
3a
3b
1
2
5:1
OAc
1
1
OH
O
O
O
O
AcO
AcO
AcO
AcO
2
3
2
84
86
6:1
4:1
OH
3c
1
1
2.5
O
O
OH
AcO
AcO
3d
4
5
2.5
2
82
81
8:1
OH
O
O
O
3e
1
AcO
AcO
AcO
AcO
10:1
6:1
O
OH
OH
O
AcO
AcO
4a
4b
6
2
89
OAc
2
2
O
O
O
O
AcO
AcO
AcO
AcO
7
8
2
82
86
9:1
OH
4c
2
2
2.5
14:1
O
O
OH
AcO
AcO
4d
9
2.5
2
80
87
12:1
22:1
OH
O
O
O
S
4e
10
2
AcO
AcO
AcO
AcO
O
SH
AcO
AcO
5a
11
1.5
91
6:1
OAc
1
1
SH
O
O
S
S
AcO
AcO
AcO
AcO
5b
Cl
12
13
2
86
89
7:1
Cl
SH
SH
5c
1
1
1.5
13:1
O
S
5d
14
1
AcO
AcO
95
17:1
(continued on next page)

6880
N. Bodipati et al. / Tetrahedron Letters 55 (2014) 6878–6881
Table 1 (continued)
Entry
Substrate
Alcohol/thiol
Time (h)
Product
Glycoside
Yielda (%)
85
a
/bb
O
SH
O
S
AcO
AcO
AcO
AcO
6a
15
1.5
4:1
OAc
2
2
SH
O
O
S
AcO
AcO
AcO
AcO
6b
16
17
2
81
85
7:1
Cl
Cl
SH
S
S
6c
2
2
1.5
12.5:1
SH
O
6d
18
1
AcO
AcO
87
20:1
a
Yields are of pure and isolated products.
b
The a
/b ratio was determined by the anomeric proton ratio from the 1H NMR (500 MHz) spectra.
Table 2
Table 2 (continued)
Tetrahydropyranylation of alcohols and phenols catalyzed by 3,5-dinitrobenzoic acida
Entry
Substrate (ROH)
Time (h)
3
Product (RO-THP)
Yieldb (%)
85
3,5-DNBA (20 mol%)
ROH
OH
O
O
OR
CH2Cl2, rt
13
8m
R = alkyl, aryl
8
7
Yieldb (%)
OH
Entry
Substrate (ROH)
Time (h)
Product (RO-THP)
OH
OH
1
2
3
2
2
2
8a
8b
8c
91
91
92
14
15
8
8
8n
8o
84
80
NO2
OH
OH
OH
OMe
4
2
8d
94
OH
5
6
2
2
8e
8f
97
98
OH
OH
OMe
OH
OH
OH
16
8
8p
81
7
8
3
6
8g
8h
88
80
OH
OMe
17
18
4
4
8q
8r
81
87
OH
OMe
9
8
4
8i
8j
86
91
a
The reactions were carried out with 1 mmol of alcohol/phenol and 1 mmol of
DHP in the presence of 0.2 mmol of 3,5-DNBA in CH2Cl2 at room temperature.
OH
b
Yields are of pure and isolated products.
10
4a–e in very high yields. In all the reactions, the
obtained predominately, as confirmed by spectroscopic data. The
predominant formation of this -anomer may arise from a thermo-
dynamic anomeric effect. Encouraged by these results, the protocol
was extended to thiols.
The 3,5-DNBA catalyzed Ferrier rearrangement of glycals 1 and
2 with thiophenol, 4-chlorothiophenol, 4-methylthiophenol, and
benzyl thiol underwent smoothly to furnish S-glycosides 5a–
a-anomer was
Br
OH
a
11
12
4
4
8k
8l
82
91
Cl
OH
dÀ6a–d in good yields and
a-anomers were obtained as major
OMe
products (Table 1).
In an effort to further explore the scope of this catalyst, we stud-
ied the tetrahydropyranylation of numerous alcohols and phenols.

N. Bodipati et al. / Tetrahedron Letters 55 (2014) 6878–6881
6881
(g) Liu, Z. J.; Zhou, M.; Min, J. M.; Zhang, L. H. Tetrahedron: Asymmetry 1999, 10,
2119–2127; (h) Nicolaou, K. C.; Mitchell, H. J. Angew. Chem., Int. Ed. 2001, 40,
1576–1624.
Initially, the tetrahydropyranylation of phenol (1 mmol) was per-
formed with dihydropyran (DHP, 7, 1 mmol) in CH2Cl2 in the pres-
ence of 20 mol % 3,5-DNBA at room temperature under aerobic
conditions for 3 h (Table 2, entry 7) to afford its tetrahydropyranyl
ether 8g in 88% yield. Using this protocol, various primary, second-
ary alcohols and phenols were transformed easily into the corre-
sponding THP-ethers 8a–r in good yields (Table 2). It is observed
that irrespective of the nature of the substitutents present on phe-
nols, THP-ethers 8g–r were obtained in good yields. Importantly,
no isomerization of double bond took place in case of eugenol
(Table 2, entry 16). Although, several reports have appeared in
the literature,25–33 most of them suffer due to the use of expensive
and moisture sensitive catalysts, high temperature, longer reaction
times, and incompatibility with other functional groups, and some
reagents also have to be prepared freshly prior to use.25–28
In conclusion, we have developed a simple and convenient
method for the synthesis of 2,3-unsaturated glycosides via the Fer-
rier rearrangement and tetrahydropyranylation. 3,5-Dinitrobenzoic
acid is an effective, very cheap, and viable catalyst in above syn-
thetic transformations with various alcohols and thiols. Thus, we
have demonstrated that 3,5-dinitrobenzoic acid is a useful organo-
catalyst in the transformations depicted herein and this methodol-
ogy is a valuable addition to modern synthetic methodologies.
3. Bussolo, V. D.; Kim, Y. J.; Gin, D. Y. J. Am. Chem. Soc. 1998, 120, 13515–13516.
4. (a) Schmidt, R. R.; Angerbauer, R. Carbohydr. Res. 1981, 89, 159–162; (b)
Angerbauer, R.; Schmidt, R. R. Carbohydr. Res. 1981, 89, 193–201.
5. (a) Tolstikov, A. G.; Tolstikov, G. A. Russ. Chem. Rev. 1993, 62, 579–601; (b) Ruiz,
J. M. J.; Obwald, G.; Petersen, M.; Fessener, W.-D. J. Mol. Catal. 2001, 11, 189–
197; (c) Bracherro, M. P.; Cabrera, E. F.; Gomez, G. M.; Peredes, L. M. R.
Carbohydr. Res. 1998, 308, 181–190.
6. Bettadaiah, B. K.; Srinivas, P. Tetrahedron Lett. 2003, 44, 7257–7259.
7. Gorityala, B. K.; Cai, S.; Lorpitthaya, R.; Ma, J.; Pasunooti, K. K.; Liu, X. W.
Tetrahedron Lett. 2009, 50, 676–679.
8. Babu, B. S.; Balasubramanian, K. K. Tetrahedron Lett. 2000, 41, 1271–1274.
9. (a) Grynkiewicz, G.; Priebe, W.; Zamojski, A. Carbohydr. Res. 1979, 68, 33–41;
(b) Bhate, P.; Horton, D.; Priebe, W. Carbohydr. Res. 1985, 144, 331–337.
10. Takhi, M.; Rahman, A.; Adel, A. H.; Schmidt, R. R. Tetrahedron Lett. 2001, 42,
4053–4056.
11. Masson, C.; Soto, J.; Bessodes, M. Synlett 2000, 1281–1282.
12. (a) Toshima, K.; Ishizuka, T.; Matsuo, G.; Nakata, M. Synlett 1995, 306–308; (b)
Shanmugasundaram, B.; Bose, A. K.; Balasubramanian, K. K. Tetrahedron Lett.
2002, 43, 6795–6798; (c) Oliviera, R. N.; Freitas, J. R. F.; Srivastava, R. M.
Tetrahedron Lett. 2002, 43, 2141–2143.
13. Yadav, J. S.; Reddy, B. V. S.; Reddy, J. S. S. J. Chem. Soc., Perkin Trans. 1 2002,
2390–2394.
14. Toshima, K.; Ishizuka, T.; Matsuo, G.; Nakata, M.; Kinoshita, M. J. Chem. Soc.,
Chem. Commun. 1993, 704–706.
15. Koreeda, M.; Houston, T. A.; Shull, B. K.; Klemke, E.; Tuinman, R. J. Synlett 1994,
90–92.
16. Lopez, J. C.; Fraser, R. B. J. Chem. Soc., Chem. Commun. 1992, 94–96.
17. Yadav, J. S.; Reddy, B. V. S.; Pandey, S. K. New J. Chem. 2001, 25, 538–540.
18. Yadav, J. S.; Reddy, B. V. S.; Reddy, K. B.; Satyanarayana, M. Tetrahedron Lett.
2002, 43, 7009–7012.
Acknowledgments
19. (a) Misra, A. K.; Tiwari, P.; Agnihotri, G. Synthesis 2005, 260–266; (b) Agarwal,
A.; Rani, S.; Vankar, Y. D. J. Org. Chem. 2004, 69, 6137–6140.
20. Hadfield, A. F.; Sartoli, A. C. Carbohydr. Res. 1982, 101, 197–208.
21. Lopez, J. C.; Gomez, A. M.; Valverde, S.; Fraser, R. B. J. Org. Chem. 1995, 60,
3851–3858.
22. (a) Rani, R.; Peddinti, R. K. Tetrahedron: Asymmetry 2010, 21, 775–779; (b)
Agarwal, J.; Peddinti, R. K. Tetrahedron: Asymmetry 2010, 21, 1906–1909; (c)
Rani, R.; Peddinti, R. K. Tetrahedron: Asymmetry 2010, 21, 2487–2492; (d)
Agarwal, J.; Peddinti, R. K. Tetrahedron Lett. 2011, 52, 117–121; (e) Agarwal, J.;
Peddinti, R. K. J. Org. Chem. 2011, 76, 3502–3505.
We gratefully acknowledge financial support from the Council
for Scientific and Industrial Research [Project No. CSIR-01(2297)/
09/EMR-II], New Delhi – India. N.B. thanks CSIR for research
fellowship.
Supplementary data
23. (a) Stevenson, C. P.; Nielsen, L. P. C.; Jacobsen, E. N. Org. Synth. 2006, 83, 162–
169; (b) But, T. Y. S.; Lu, J.; Toy, P. H. Synlett 2010, 1115–1117.
24. For papers involving co-crystals of 3,5-DNBA, see: (a) Ranganathan, A.;
Pedireddi, V. R. Tetrahedron Lett. 1998, 39, 1803–1806; (b) Pedireddi, V. R.;
Ranganathan, A.; Chartterjee, S. Tetrahedron Lett. 1998, 39, 9831–9834; (c)
Pedireddi, V. R.; PrakashaReddy, J. Tetrahedron Lett. 2002, 43, 4927–4930; (d)
Supplementary data (experimental details and products charac-
terization for compounds 3a–3e, 4a–4e, 5a–5e, 6a–6e, and 8a–8r)
associated with this article can be found, in the online version, at
http://dx.doi.org/10.1016/j.tetlet.2014.10.093.
´
Sikorski, A.; Trzybinski, D. Tetrahedron Lett. 2014, 55, 2253–2255.
25. Miyashita, M.; Yoshikoshi, A.; Grieco, P. A. J. Org. Chem. 1977, 42, 3772–3774.
26. Namboodiri, V. V.; Varma, R. S. Tetrahedron Lett. 2002, 43, 1143–1146.
27. Karimi, B.; Maleki, J. Tetrahedron Lett. 2002, 43, 5353–5355.
28. Khan, A. T.; Choudhury, L. H.; Ghosh, S. Tetrahedron Lett. 2004, 45, 7891–7894.
29. Khan, A. T.; Ghosh, S.; Choudhury, L. H. Eur. J. Org. Chem. 2005, 4891–4896.
30. Pachamuthu, K.; Vankar, Y. D. J. Org. Chem. 2001, 66, 7511–7513.
31. Naik, S.; Gopinath, R.; Patel, B. K. Tetrahedron Lett. 2001, 42, 7679–7681.
32. Hon, Y. S.; Lee, C. F.; Chen, R. J.; Szu, P. H. Tetrahedron 2001, 57, 5991–6001.
33. Yadav, J. S.; Reddy, B. V. S.; Gnaneshwar, D. New J. Chem. 2003, 27, 202–204.
References and notes
1. Williams, N. R.; Wander, J. D. The Carbohydrates in Chemistry and Biochemistry;
Academic Press: New York, 1980; p 761.
2. (a) Ferrier, R. J. Adv. Carbohydr. Chem. Biochem. 1969, 24, 199–266; (b) Schmidt,
R. R.; Angerbauer, R. Carbohydr. Res. 1979, 72, 272–275; (c) Fraser, R. B. Acc.
Chem. Res. 1985, 18, 347–354; (d) Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 93,
1503–1531; (e) Dorgan, B. J.; Jackson, R. F. W. Synlett 1996, 859–861; (f)
Danishefsky, S. J.; Bilodeau, M. T. Angew. Chem., Int. Ed. 1996, 35, 1380–1419;