ZnBr2-catalyzed and microwave-assisted synthesis of 2,3-unsaturated glucosides of hindered phenols and alcohols

Article abstract of DOI:10.1080/00397911.2014.909490

GRAPHICAL ABSTRACT Zinc bromide (ZnBr₂) under microwave irradiation efficiently catalyzed the Ferrier reaction of hindered phenols and alcohols to afford the corresponding α-2,3-unsaturated glucoside acetates in good yields and with good stereoselectivity. The reaction affords a facile access to new 2,3-dideoxyglucosides of important phenolic and alcoholic constituents of spices.

Full text of DOI:10.1080/00397911.2014.909490

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ZnBr2-Catalyzed and Microwave-Assisted
Synthesis of 2,3-Unsaturated Glucosides
of Hindered Phenols and Alcohols
D. James Bound a , B. K. Bettadaiah a & P. Srinivas a
a Plantation Products, Spices and Flavour Technology Department ,
CSIR-Central Food Technological Research Institute , Mysore , India
Accepted author version posted online: 21 May 2014.Published
online: 02 Jul 2014.
To cite this article: D. James Bound , B. K. Bettadaiah & P. Srinivas (2014) ZnBr2-Catalyzed and
Microwave-Assisted Synthesis of 2,3-Unsaturated Glucosides of Hindered Phenols and Alcohols,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 44:17, 2565-2576, DOI: 10.1080/00397911.2014.909490
To link to this article: http://dx.doi.org/10.1080/00397911.2014.909490
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Synthetic Communications1, 44: 2565–2576, 2014
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2014.909490
ZnBr2-CATALYZED AND MICROWAVE-ASSISTED
SYNTHESIS OF 2,3-UNSATURATED GLUCOSIDES
OF HINDERED PHENOLS AND ALCOHOLS
D. James Bound, B. K. Bettadaiah, and P. Srinivas
Plantation Products, Spices and Flavour Technology Department,
CSIRꢀCentral Food Technological Research Institute, Mysore, India
GRAPHICAL ABSTRACT
Abstract Zinc bromide (ZnBr2) under microwave irradiation efficiently catalyzed the Fer-
rier reaction of hindered phenols and alcohols to afford the corresponding a-2,3-unsaturated
glucoside acetates in good yields and with good stereoselectivity. The reaction affords a
facile access to new 2,3-dideoxyglucosides of important phenolic and alcoholic constituents
of spices.
Keywords Alcohols; Ferrier reaction; microwave; phenols; 2,3-unsaturated 1-O-gluco-
sides; ZnBr2
INTRODUCTION
2,3-Unsaturated 1-O-glycosides are useful intermediates in the total synthesis
of several bioactive molecules as the double bond in the pyran ring can be trans-
formed by hydrogenation, epoxidation, dihydroxylation, or aminohydroxylation
reactions.[1] Also, extension of the scope of the Ferrier reaction by fragmentation–
rearrangement reactions of selectively substituted 1,2-cyclopropanated glucose deri-
vatives has been reported recently.[2] Ferrier reaction, involving the reaction of
3,4,6-tri-O-acetyl glycals with alcohols or phenols, is employed for the synthesis of
corresponding 2,3-unsaturated 1-O-glycosides.[3] The reaction involves a cyclic
Received January 23, 2014.
Address correspondence to P. Srinivas, Plantation Products, Spices and Flavour Technology
Department, CSIRꢀCentral Food Technological Research Institute, Mysore 570 020, India. E-mail:
pullabhatla_s@yahoo.co.uk
2565

2566
D. J. BOUND, B. K. BETTADAIAH, AND P. SRINIVAS
allyloxocarbenium intermediate formed via displacement of the acetyl group in
glucal, followed by nucleophilic attack from the quasiequatorial orientation.[4]
A
wide range of catalysts comprising Lewis acids (BF3 ꢁ Et2O,[5] La(NO3)3,[6] LiBF4[7]),
oxidizing reagents (I2,[8] iodine dicollidine perchlorate [IDCP],[9] 2,3-dichloro-5,6-
dicyanobenzoquinone [DDQ],[10] N-iodosuccinimide [NIS],[11] trichloroacetimidate,[12]
ceric ammonium nitrate [CAN],[13] HClO4[14]), and inorganic acids (montmorillonite
K-10,[15] NaHSO4[16] on silica gel) have been reported to promote this transformation.
Also, several metal triflates of scandium,[17] aluminum,[18] tetramethylsilane (TMS),[19]
ytterbium,[20] dysprosium,[21] and erbium[22] have used effectively for the Ferrier
[23]
reaction. More popular catalysts include mainly indium salts (InCl3 and InBr3[24]),
as well as other metal halides including FeCl3,[25] BiCl3,[26] ZnCl2,[27] ZrCl4,[28] NbCl5,[29]
and SnCl4.[30] Ferrier rearrangement has been carried out also under microwave
irradiation for preparation of O-glycosides of alcohols using montmorillonite K-10,[31]
ferric sulfate hydrate,[32] NbCl5,[29] silica gel,[33] and C-glycosides from trialkylsilanes
and glucal using InCl3.[34] Recently, metal-free conditions have been employed for the
Ferrier reaction in hexafluoroisopropanol, where the solvent promoted glycosylation.[35]
In the Ferrier reaction of phenols with tri-O-acetyl-D-glucal, formation of C-glycosides
has been reported, especially in the case of hindered phenols.[36,37]
In our earlier efforts to synthesize 2,3-unsaturated glucosides of terpene
alcohols, we found ZnCl2 catalyzed the Ferrier reaction of tertiary, allyl, and benzyl
alcohols with 3,4,6-tri-O-acetyl-D-glucal in CH2Cl2.[27] However, the reactions were
slow and afforded both the a- and b-isomers. In the present study, we aimed at the
preparation new water-soluble 2,3-unsaturated glucosides of carvacrol and thymol,
the phenolic constituents of spices (oregano and ajowan, respectively). These
phenols, apart from having characteristic flavor properties, possess potent antimicro-
bial activity, against even several drug-resistant bacteria.[38] The presence of bulky
alkyl substituents in the aromatic ring in phenols does pose a challenge in terms
of longer reaction times and unsatisfactory yields.[39] In this report, reaction of
2,6-dimethylphenol, a phenol with substituent in the ortho position, with 3,4,
6-tri-O-acetyl-D-glucal using montmorillonite K-10 catalyst, afforded a poor yield
of the O-aryl glycoside.
RESULTS AND DISCUSSION
During the course of our investigation, we found that the reaction of 3,4,6-
tri-O-acetyl-D-glucal with carvacrol and thymol in the presence of various catalysts
such as PTSA, InCl3, ZnCl2, montmorillonite K-10, and BF3ꢁOEt2 resulted in little
product formation. Only when ZnBr2 was used as the catalyst in the reaction under
ambient conditions was the formation of a product observed, but the reaction was
incomplete even after 8 h. Under reflux conditions, it afforded a mixture of products.
Recently, we reported microwave-assisted substitution of SN1-active halides with
ambident thiocyanate nucleophile, in the form of its zinc salt, wherein formation
of thiocyanates in shorter reaction times with greater yields and regioselectivity
was observed.[40] Also, microwave facilitates a number of organic reactions such
as aromatic nucleophilic substitution of 4,7-dichloroquinoline and 2-chloroben-
zothiazole with aromatic and aliphatic amines,[41] cyclocondensations in heterocyclic
synthesis,[42,43] and synthesis of nitriles from aldehydes.[44] In the present study, we

2,3-UNSATURATED GLUCOSIDES OF PHENOLS AND ALCOHOLS
2567
discovered that microwave irradiation facilitated the ZnBr2-catalyzed reaction of
carvacrol with glucal. A concentration of 10 mol% of the catalyst was found to be
optimum. Of the several solvents (CH2Cl2, CHCl3, CCl4, CH3CN, and 1, 4-dioxane,
Table 1) employed for the reaction, chloroform afforded the best results with faster
reaction time (25 min) and preponderant formation of the a-isomer of the corre-
sponding 2,3-unsaturated glucoside acetate (entry 5, Table 2). Microwave power
of 400 W was found to be most suitable in terms of reaction times and product yields.
Reaction of thymol also progressed rapidly (20 min) to afford the a-anomeric pro-
duct in good yield and stereoselectivity (entry 6). While the formation of
C-glycosides was observed in earlier cases of the phenolic substrates with bulky sub-
stituents in the ortho position,[36,37] no such formation of C-glucosides occurred in
the present reaction. The synthetic protocol using ZnBr2 in chloroform using micro-
wave irradiation was then further investigated with phenol (entry 1) and cresols
(entries 2–4). All the reactions proceeded smoothly, with the p-cresol affording the
corresponding a-glucoside acetate exclusively in shorter reaction time (15 min) and
greater yield (79%). The present reaction was found to progress well with other phe-
nols having alkyl substituents, namely, 4-ethyl (entry 7) and 3,4-dimethyl (entry 8),
resulting in the formation of products in very good yields (74–75%) with good
stereoselectivity. The reaction was slower in the case of phenols with an
electron-withdrawing group such as –NO2 at the para position (entry 10) and the
yield also was lesser (57%). The reaction was faster (20 min), and the product yield
was excellent (entry 9) in the presence of an electron-donating group such as
–OMe in the para position. However, in the case of both 2-methoxy and 3-methox-
yphenols, the reaction did not occur even after prolonged reaction time (2 h). A simi-
lar observation was made in the case of eugenol and vanillin, wherein the aromatic
ring had phenolic hydroxy and methoxy groups in the position ortho to each other.
After the optimization of the Ferrier reaction with phenols, the reactions
between tri-O-acetyl-D-glucal and various primary, secondary, tertiary, allyl, and
Table 1. Optimization of solvent for ZnBr2-catalyzed and microwave-assisted Ferrier reaction of carva-
crol, a phenol, as a model substrate
Entry
Solvent
Reaction time
Yield (%)
a=b ratio
1
2
3
4
5
CH2Cl2
CCl4
CHCl3
120
40
25
60
60
45
75
70
4.7:1
5:1
8.5:1
a
—
a
CH3CN
1,4-Dioxan
—
—
a
a
—
aNo product formation.

2568
D. J. BOUND, B. K. BETTADAIAH, AND P. SRINIVAS
Table 2. ZnBr2-catalyzed and microwave-assisted synthesis of 2,3-unsaturated 1-O-glucoside acetates of
phenols
Time
Yield
Entry
1
Phenols
Product
(min) (%)a (a=b)b
30
30
89 (10:1)
75 (8:1)
2
3
4
20
15
70 (10:1)
79 (1:0)
5
25
70 (8.5:1)
6
20
56 (13:1)
7
8
20
25
74 (7:1)
75 (1:0)
(Continued )

2,3-UNSATURATED GLUCOSIDES OF PHENOLS AND ALCOHOLS
2569
Table 2. Continued
Time
Yield
Entry
Phenols
Product
(min) (%)a (a=b)b
9
20
45
83 (1:0)
57 (1:0)
10
aIsolated yields.
1
bRatio was determined by integration of the anomeric protons in H NMR spectra of crude products.
benzyl alcohols as glycosyl acceptors were investigated under the standardized
conditions. The structure and stereochemistry of all the glucoside acetates were
characterized by 1H NMR, 13C NMR, infrared (IR), and high-resolution mass spec-
trometry (HRMS) data. The stereoselectivity (a=b ratio) in all the reactions was deter-
mined by on the basis of integrated values of anomeric protons in 1H NMR spectra of
the products with protons for a- and b-isomers appearing in the 5.6–5.7 and
5.7–5.8 ppm ranges respectively for the crude products. This synthetic protocol
afforded corresponding 2,3-unsaturated glucoside acetates of alcohols in good yields
and good anomeric selectivity (Scheme 1, Tables 3–5). The simple primary alcohols
gave the products in excellent yields (82–96%, Table 3) and high stereoselectivity
(2:1 to 10:1). In the case of secondary alcohols (Table 4), the reaction was also stereo-
selective with preponderant formation of the glucosides in good yields (66–95%).
The synthetic protocol could be conveniently applied to the preparation of 2,
3-unsaturated glucoside acetates of several sterically hindered secondary terpene alco-
hols (menthol, borneol, and fenchol, entries 5–7, Table 4). Reaction with tertiary
Scheme 1. Synthesis of 2,3-unsaturated 1-O-glucoside acetates of phenols and alcohols.

2570
D. J. BOUND, B. K. BETTADAIAH, AND P. SRINIVAS
Table 3. ZnBr2-catalyzed and microwave-assisted synthesis of 2,3-unsaturated 1-O-glucoside acetates of
10 alcohols
Time
(min)
Yield
(%)a (a=b)b
Entry
1
Alcohol
Product
30
85 (2:1)
2
3
15
30
89 (7:1)
96 (7:1)
4
5
6
30
40
80
90 (6:1)
96 (6:1)
82 (7:1)
7
8
9
30
120
90
96 (7:1)
89 (10:1)
96 (5:1)
10
15
95 (7:1)
aIsolated yields.
bRatio was determined by integration of the anomeric protons in H NMR spectra of crude products.
1

2,3-UNSATURATED GLUCOSIDES OF PHENOLS AND ALCOHOLS
2571
Table 4. ZnBr2-catalyzed and microwave-assisted synthesis of 2,3-unsaturated 1-O-glucoside acetates of
2o alcohols
Time
(min)
Yield
(%)a (a=b)b
Entry
Alcohol
Product
1
15
15
89 (6:1)
2
89 (20:1)
3
4
10
40
95 (12:1)
66 (—c)
5
30
93 (1:0)
6
15
87 (1:0)
7
30
88 (1:0)
aIsolated yields.
1
bRatio was determined by integration of the anomeric protons in H NMR spectra of crude products.
cAnomeric ratio could not be deciphered.

2572
D. J. BOUND, B. K. BETTADAIAH, AND P. SRINIVAS
Table 5. ZnBr2-catalyzed and microwave-assisted synthesis of 2,3-unsaturated 1-O-glucoside acetates of
SN1- active (allyl, benzyl, and tertiary) alcohols
Time
(min)
Yield
(%)a (a=b)b
Entry
1
Alcohol
Product
10
89 (5:1)
89 (1:0)
2
120
3
4
180
93 (1:0)
25
93 (3:1)
5
6
7
30
15
45
76 (1:0)
60 (1:0)
70 (1:0)
8
55
56 (1:0)
aIsolated yields.
bRatio was determined by integration of the anomeric protons in H NMR spectra of crude products.
1

2,3-UNSATURATED GLUCOSIDES OF PHENOLS AND ALCOHOLS
2573
alcohols (entries 5–8, Table 5) afforded products in 56–76% yields. This was also
demonstrated with a-terpineol and 4-terpinenol, tertiary terpene alcohols with good
steric hindrance at the nucleophilic center, where the corresponding a-2,3-unsatu-
rated glucoside acetates formed exclusively in 70% and 56% yields respectively. In
these cases, reduction of the microwave power from 400 W to 200 W minimized the
competitive dehydration reaction and improved product yields. In the case of other
SN1-active substrates, allyl and benzyl alcohols, the reaction afforded the correspond-
ing 2,3-unsaturated glucoside acetates in excellent yields (89–93%) with good
stereoselectivity (Table 5). The reaction with R-(þ) and S-(–)-perillyl alcohols (entries
2 and 3, Table 5) gave the corresponding a-anomeric products in good yields.
In summary, a facile, rapid, and general synthetic procedure involving micro-
wave irradiation and a new efficient ZnBr2 catalyst in type I Ferrier rearrangement
has been developed for the stereoselective preparation of a-2,3-unsaturated glucoside
acetates of phenols, especially the ones with steric hindrance. The reaction
was stereoselective with alcohols as demonstrated by the preponderant formation of
a-glucoside acetates of various primary, secondary, tertiary, allyl, and benzyl alcohols.
EXPERIMENTAL
ZnBr2, 3,4,6-tri-O-acetylglucal, alcohols, and phenols employed in the study
were procured from Sigma Aldrich (St. Louis, MO, USA). Chloroform used for
˚
the reaction was distilled, stored over molecular sieves (5 A), and passed over anhy-
drous sodium sulfate prior to use. All reactions were performed in a microwave reac-
1
tor (Milestone lab-station, model START S, Italy). H and 13C NMR spectra were
recorded on a 500-MHz NMR spectrometer (Bruker Avance, Reinstetten, Germany)
using CDCl3 solvent. Chemical shifts (d) are reported in parts per million (ppm) rela-
tive to tetramethylsilane (TMS) as the internal standard, and coupling constants (J)
are reported in hertz (Hz). Multiplicities are reported as s (singlet), d (doublet), t
(triplet), q (quartet), m (multiplet), bs (broad singlet), and sp (septet). IR spectra were
recorded on a Fourier transform (FT) Raman Nicolet 5700 spectrometer as a sample
smear on KBr prism for liquid samples or as a KBR pellet for solid samples. Mass
spectral (MS) analyses of compounds were carried out using MS (Waters Q-Tof
Ultima, Manchester, UK) in the electrospray ionization (ESI) positive mode. Spe-
cific rotations of compounds were calculated from observed optical rotations
recorded for methanolic solutions of compounds on a Perkin-Elmer 243 model
polarimeter. Melting points were measured on a Gallenkamp apparatus using glass
capillary tubes and are uncorrected. Thin-layer chromatographic (TLC) analysis was
performed on silica gel 60 F254(Merck, Germany) coated on alumina sheet with 5%
and 20% ethyl acetate in petroleum ether (60–80 ꢂC) as the developing solvent. The
compounds were visualized by ultraviolet (UV) light (254 and=or 366 nm) and=or by
staining with iodine and phosphomolybdic acid.
General Procedure for Synthesis of Alkyl and Phenyl 2,3-Dideoxy-a-
D-erythro-hex-2-enopyranoside Acetates
In a typical reaction (Scheme 1), anhydrous ZnBr2(0.5 mmol) was added to a
mixture of 3,4,6- tri-O-acetyl glucal (5 mmol) and a phenol or alcohol (4.5 mmol)

2574
D. J. BOUND, B. K. BETTADAIAH, AND P. SRINIVAS
in CHCl3(8 mL). A Teflon heating button and a stirring bar were introduced into the
flask, which was then equipped with condenser and irradiated with microwave radi-
ation (400 W) under open-vessel conditions in a Milestone START-S microwave lab
station at 72 ꢂC for a specified time period (Tables 1–5). After the completion of the
reaction, water (15 ml) was added to the reaction mixture and the organic layer was
separated. The aqueous layer was extracted with chloroform (2 ꢃ 5 ml). The com-
bined organic layers was dried over anhydrous Na2SO4 and concentrated to afford
a syrupy crude mass, which was refined by column chromatography on silica gel
(100–200 mesh) using ethyl acetate (5–10%) in petroleum ether (60–80 ꢂC) as the elu-
ent. The ratio of a and b anomers, which had close Rf values and eluted together,
1
was determined by integration of the corresponding hydrogen signals in the H
NMR of the crude product.
Characterization Data for Products 3e and 3f
5-Isopropyl-2-methylphenyl
4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-
hex-2-eno-pyranoside (3e). Colorless viscous liquid; [a] D þ 126.02ꢂ (c ¼ 1.96,
1
CH3OH, a=b ¼ 8.5:1); H NMR (500 MHz, CDCl3): d 1.23 (d, J ¼ 6.89 Hz, 6H),
2.01 (s, 3H), 2.12 (s, 3H), 2.20 (s, 3H), 2.87 (sp, J ¼ 6.89 Hz, 1H), 4.16 (dd,
J ¼ 11.5, 1.5 Hz, 1H), 4.26–4.33 (m, 2H), 5.39 (d, J ¼ 9.50 Hz, 1H), 5.67 (bs, 1H),
6.01 (bs, 2H), 6.84 (dd, J ¼ 7.66, 1.3 Hz, 1H), 7.06 (m, 2H); 13C NMR
(CDCl3,125 MHz): 170.46, 169.98, 155.26, 147.88, 130.26, 129.61, 127.10, 124.84,
119.83, 113.67, 93.31, 67.51, 64.83, 62.59, 33.68, 23.79, 20.68, 20.40, 15.62; IR (film,
cmꢀ1): 3471, 3054, 3023, 2961, 2928, 2871, 1759, 1651, 1613, 1579, 1456, 1369, 1336,
1236, 868, 790, 763; HRMS (ESI) m=z: [Mþ þ Na] calcd. for C20H26O6Na 385.1620;
found 385.1594.
2-Isopropyl-5-methylphenyl
4,6-di-O-acetyl-2,3-dideoxy-a-D-erythro-
hex-2-eno-pyranoside (3f). Colorless viscous liquid; [a] D þ 103.26ꢂ (c ¼ 1.53,
1
CH3OH, a=b ¼ 13:1); H NMR (500 MHz, CDCl3): d 1.22 (d, J ¼ 6.90 Hz, 3H),
1.23 (d, J ¼ 6.90 Hz, 3 H), 2.04 (s, 3H), 2.14 (s, 3H), 2.34 (s, 3H), 3.28 (sp, J ¼ 6.9 Hz,
1H), 4.17 (dd, J ¼ 12.0, 2.17 Hz, 1H), 4.24–4.36 (m, 2H), 5.43 (dd, J ¼ 9.70, 1.0 Hz,
1H), 5.68 (bs, 1H), 6.04 (bs, 2H), 6.85 (d, J ¼ 7.63 Hz, 1H), 7.06 (s, 1H), 7.13 (d,
J ¼ 7.71 Hz, 1H); 13C NMR (CDCl3,125 MHz): 170.44, 169.96, 154.19, 136.23,
134.69, 129.50, 127.04, 125.68, 122.92, 115.92, 93.13, 67.61, 64.82, 62.46, 26.46,
22.71, 22.54, 20.93, 20.66, 20.36; IR (film, cmꢀ1): 3471, 3059, 2962, 2927, 2870,
1757, 1613, 1577, 1369, 1339, 1235, 791, 767. HRMS (ESI) m=z: [Mþ þ Na] calcd.
for C20H26O6 385.1620; found 385.1635.
ACKNOWLEDGMENTS
The authors thank Ram Rajasekharan, Director, CFTRI, for his support and
constant encouragement for the work, and appreciate the help from J. R. Manjunatha,
Technical Officer, Plantation Products, Spices and Flavour Technology Department,
CFTRI, for NMR studies of compounds. Padmere Mukund Lakshman and M. Asha,
Central Instruments Facility and Services Department, CFTRI, are acknowledged for
their assistance in HRMS and IR analyses.

2,3-UNSATURATED GLUCOSIDES OF PHENOLS AND ALCOHOLS
2575
FUNDING
D. J. B. is grateful to the Council of Scientific and Industrial Research,
New Delhi, for the award of a Senior Research Fellowship.
SUPPLEMENTARY DATA
Supplemental data for this article can be accessed on the publisher’s website.
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