One-pot Mukaiyama type carbon-Ferrier rearrangement of glycals: Application in the synthesis of chromanone 3-C-glycosides

Article abstract of DOI:10.1016/j.carres.2016.11.018

One-pot carbon-Ferrier rearrangement of glycals with unactivated aryl methyl ketones has been developed under mild Silyl triflate catalysis. Keto methyl group of various aryl methyl ketones without being converted into silyl enol ether could directly attack anomeric position of glycals to form keto functionalized C-glycosides in moderate to good yields with high α-selectivity. The versatility of this method has been extended to the synthesis of a small library of chromanone 3-C-glycosides.

Full text of DOI:10.1016/j.carres.2016.11.018

Accepted Manuscript
One-pot Mukaiyama type carbon-Ferrier rearrangement of glycals: Application in the
syntheses of chromanone 3-C-glycosides
Ashutosh K. Dash, Tatina Madhubabu, Syed Khalid Yousuf, Sushil Raina, Debaraj
Mukherjee
PII:
S0008-6215(16)30252-X
10.1016/j.carres.2016.11.018
CAR 7301
DOI:
Reference:
To appear in: Carbohydrate Research
Received Date: 23 July 2016
Revised Date: 12 November 2016
Accepted Date: 29 November 2016
Please cite this article as: A.K. Dash, T. Madhubabu, S.K. Yousuf, S. Raina, D. Mukherjee, One-pot
Mukaiyama type carbon-Ferrier rearrangement of glycals: Application in the syntheses of chromanone
3-C-glycosides, Carbohydrate Research (2016), doi: 10.1016/j.carres.2016.11.018.
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ACCEPTED MANUSCRIPT
One-pot Mukaiyama type carbon-Ferrier rearrangement of glycals:
Application in the syntheses of chromanone 3-C-glycosides
Ashutosh K. Dash,a Madhubabu Tatina,b Syed Khalid Yousuf, c Sushil Raina b and Debaraj
Mukherjee*a
ꢀ TBSOTf acts both as glycosylating and silylating agent
ꢀ In situ silylenol ether formation
ꢀ Avoidance of hazardous alkyl lithiums as strong base and cryogenic condition
ꢀ Highly stereoselective glycosylation
ꢀ Application in the syntheses of chromanone-3-C-glycosides

ACCEPTED MANUSCRIPT
One-pot Mukaiyama type carbon-Ferrier rearrangement of glycals: Application in the
syntheses of chromanone 3-C-glycosides
Ashutosh K. Dash,a Madhubabu Tatina,b Syed Khalid Yousuf, c Sushil Raina b and Debaraj
Mukherjee*a
aNatural Product Chemistry Division, Indian Institute of Integrative Medicine, Jammu,180001,
CSIR-India, Academy of Scientific and Innovative Research
bNatural Product Chemistry Division, Indian Institute of Integrative Medicine, Jammu,180001,
CSIR-India
cNatural Product Chemistry Division, Indian Institute of Integrative Medicine, Kashmir,180001,
CSIR-India
A B S T R A C T
One-pot carbon-Ferrier rearrangement of glycals with unactivated aryl methyl ketones has been
developed under mild Silyl triflate catalysis. Keto methyl group of various aryl methyl ketones
without being converted into silyl enol ether could directly attack anomeric position of glycals to
form keto functionalized C-glycosides in moderate to good yields with high α-selectivity. The
versatility of this method has been extended to the synthesis of a small library of chromanone 3-
C-glycosides.
Key Words
Carbon-Ferrier rearrangement, chromanone 3-C-glycosides, acetophenones, 2,3-unsaturated
glycosides, Lewis acid, glycopyranosides
1. Introduction
The Ferrier rearrangement involves a reaction of suitably protected 1,2-glycals with nucleophiles
under Lewis acid catalysis to form the corresponding 2,3-unsaturated glycosides after
concomitant loss of a substituent at C-3.1 The carbon-Ferrier rearrangement utilizes carbon
nucleophiles such as allylsilanes,2 silyl cyanides,3 silyl ketene acetals,4 olefins,5 aromatic

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nucleophiles,6 unactivated alkynes,7 isocyanides,8 etc, in the presence of a Lewis acid catalyst to
form the corresponding 2,3-unsaturated glycosides. When α-methylene carbons of ketones have
been used as carbon nucleophiles for carbon-Ferrier reaction, their downstream glycosides can
be served as intermediates in the synthesis of a large number of biologically important natural
products such as Aspergillide,9 Quercetin,10 Myricetin,11 Kampferol,12 etc. Generally, ketones
with α-methylene groups are converted into corresponding silyl enol ether which then undergo
carbon-Ferrier rearrangement under various Lewis acids such as BF3-Et2O,13 TFA,14 TMSOTf, 15
LiClO4,16 Yb(OTf)3,17,18 H3PO4,19 iodinium catalyst,20 InCl3,21 FeCl3,22 HClO4,23 etc. Although
an efficient protocol for C-glycosylation, the major drawback of the above methods lies in the
preparation of silyl enol ether which in many cases requires hazardous reagents like alkyl
24
lithiums, under cryogenic conditions (Scheme 1). It is therefore desirable to have a direct
method where α−carbon of ketone can directly attack anomeric carbon in carbon-Ferrier
rearrangement via in situ generated silyl enol ether (Scheme1). With our interest in C-
glycosylation using glycals,25 herein we report a one pot carbon-Ferrier reaction with aryl methyl
ketones and its application in the synthesis of chromanone C-glycosides.
Scheme1: Synthesis of α-keto functionalized glycopyranosides
TMSOTf is a common and readily available silyl triflate used extensively in organic syntheses,
26, 27. Downey et al. have used a combination of TMSOTf and DIPEA for a variety of reactions
e.g. Mukaiyama aldol reaction, addition of catalytically generated zinc acetylides to aldehydes or
N-phenyl nitrones, addition of acetylides as wells as thiols to benzylic methyl ethers and
dimethyl acetals.28

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2. Result and discussion
In order to develop an optimum procedure for the carbon-Ferrier rearrangement, we first tried the
conditions as per a reported method.29 When Lewis acid (0.1 eqv.) and base (0.2 eqv.) was used
we got very poor yield of about 20% of the desired product. The yield was abruptly increased
when TBSOTf was examined as silyl triflate in the presence of iPr2NEt as amine base in DCM
instead of acetonitrile. After experimenting with silyl triflate, bases and solvents we obtained a
condition where starting material 3,4,6-tri-O-acetyl-D-glucal (1) was completely consumed. The
reaction proceeded smoothly in 30 minutes and exclusively furnished the required product, 1a
with a satisfactory yield up to 68%. Prolonging the reaction time resulted in the degradation of
the products. The results are summarized in the Table 1 below. Use of TBSOTf (1.25 eqv.), i-
Pr2NEt (1.20 eqv.) in DCM (5ml/mmol) as solvent (Table 1, entry 6) was found to be optimum
for the transformation.
Table.1 Optimization of C-glycosylation
Entry Silyl triflate (eqv.)
Base (eqv.)
i-Pr2NEt (0.2)
Et3N (0.1)
Solvent
DCM
Yieldb (%)
1.
2.
3.
4.
5.
6.
TMSOTf (0.1)
TMSOTf (0.2)
TMSOTf (1)
20
22
25
33
55
CH3CN
CH3CN
CH3CN
DCM
Et3N (0.5)
TMSOTf (1.0)
TBSOTf (1.25)
TBSOTf (1.25)
Et3N (1.0)
Et3N(1.20)
iPr2NEt(1.20)
DCM
68
b
aGlucal (1.0 eqv.), Acetophenone (1.05 eqv.), solvent (5 mL/mmol of glucal). Isolated
yields after column chromatography.

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With the optimized condition at our disposal, the generality of the method was established by
reacting a series of substituted acetophenones and protected glycals to provide the desired
glycosides in moderate to good yields (Table 2). In general, reaction times for
diacetate (3) were found to be lower than that of -glucal triacetate (1) and -Galactal triacetate
(2). The Ferrier products (1a-2d) obtained from -sugars were α−C glycosides while the
products (3a-3d) derived from
-sugars were β which is in agreement with the earlier reports.30
L-rhamnal
D
D
D
L
The cause of stereoselectivity probably depends on the stereochemistry of the substituent at C3
of glycal.30a 1H NMR spectra of the synthesized products were compared with values reported in
the literature.31
Table-2: Condensation of glycals with substituted acetophenone under optimized
conditiona
Glycalsb
1
2
3
C-Glycopyranosidesc
1a 66%
1b 55%
1c 56%

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1d 67 %
1e 68%
1f 60%
2a 69%
2b 60%
2c 66%
2d 69%
3a 49%
3b 53%
3c 59%
3d 62%
aReaction conditions: Sugar partner (1 eqv.), acetophenone (1.05 eqv.), TBSOTf (1.25 eqv.), i-
b
Pr2NEt (1.20 eqv.), DCM as solvent (5mL/mmol); All C-glycosides derived from
D
-glucal
-rhamnal diacetate yielded
exclusive β-glycosidic linkage; cIsolated yield after column chromatography.
triacetate and
D-galactaltriacetate are α glycosides whereas L

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After the successful scope studies by obtaining glycosylated acetophenones, we set forth for an
application of our work to synthesize chromanone-C-3-glycosides. The most abundant flavonoid
glycosides in plants are flavone O/C-glycosides. Among them the glycosides found typically in
nature are 3- or 7-O-glycosides. But when biological activity is taken into consideration, C-
glycosides have proven better than O-glycosides.32 Hence we have made an effort for the
synthesis of chromanone C-glycosides. In place of aryl methyl ketone (scheme-1) if chromanone
can be incorporated, isoflavone-C-glycosides mimicking structures can be easily achieved. As
reported Chromanone-C-glycoside is an important class of compounds widely distributed in
nature33 which plays variety of essential roles in the growth and development of plants.34 They
also posses miscellaneous biological activities such as antioxidant,35 antidiabetic,36
antinflammatory,37 antibacterial and antifungal activities,38 antitumour,39 immunomodulatory
activity,40 etc. It is highly desirable to have practical methods for the synthesis of Chromanone-
C-glycoside to be able to explore their potential as biologically active molecules; we have
prepared a small library of chromanone-C-glycoside by using our method.
By following our strategy, synthesis of C-glycosides of chromanones can be accomplished by
using Mukaiyama type reaction of 4-chromanone with glycals in one-pot where carbon-carbon
bond formation takes place with glycoside precursors at various carbons of chromanones in a
substituent-dependant manner. On this prospect, we reacted, 2,2-dimethyl-4-benzopyranone (5)
with the glycal partner (1) keeping all other variables fixed under previously optimized condition
(entry 6, Table 1), which afforded us a diastereomeric mixture 1g. The ratio of isomers was
calculated from crude NMR. Fortunately we were able to separate the major one from the
mixture 1g with a satisfactory yield (66%). (scheme2)
OAc
O
OAc
O
AcO
AcO
AcO
O
O
O
O
TBSOTf
(1.25eqv.)
i-Pr2NEt (1.20 eqv)
DCM, 0 oC-rt
5
1g
Scheme2: Synthesis of chromanone-3-C-glycoside

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Spectroscopic analysis demoed the appearance of a new chemical shift at δ 2.76 (1H) and 62.12
(CH) with concomitant loss of the methylene signal at δ 2.73 (2H) and 48.36 (CH2) respectively
1
13
in H and C NMR for group signifying the attachment of sugar moiety at C3. Substrate scope
for the chromanone-C-glycoside (Table 3) was done by taking four different sugar partners (1a,
1b, 1c, 1d of Table 3) with three different chromanones (5, 6 & 7 of Table 3). It is pertinent to
mention that all C-3 chromanone glycosides were obtained as mixture of diastereomers ratio of
1
which were calculated from crude H NMR and major diastereomers were purified through
column. However when 7-methoxy group is attached to 4-chromanone, the glycal partner was
coupled at C-6 position (1h) indicating the substituent effect. In case of 4-hydroxy coumarin (7),
it was interesting to note that 0.25eqv. of TBSOTf was enough to catalyze the reaction and
provide the product 1i in 88% yield. Overall, the present methodology provides an easy access to
the compounds like 1g, 3e and 1i and analogs and derivatives thereof, their biological activities
like anti-inflammatory, anti-cancer, anti-bacterial, anti-fungal, etc. will be evaluated and
published elsewhere.
Table-3: Condensation of glycals with substituted Chromanones under optimized
conditiona to form C-glycopyranosides.
Glycalsb
1
2
3
4
Chromanones

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5
6
7
Chromanone C-glycosidesc
1g 66% dr =4:1
2e 68% dr =3:1
3e 67% dr =4:1
OAc
O
AcO
O
O
H3CO
4a 55% dr =3:1
1h 70%
1i 88%
aReaction conditions: Sugar partner (1.1 eqv.), Chromans (1.05 eqv.), TBSOTf (1.25 eqv.), i-
Pr2NEt (1.20 eqv.), reaction temperature 0-30°C, CH2Cl2 as solvent (5mL/mmol); btime taken for
c
protected glucal and galactal was 30 min while for rhamnal it was 10 mins; isolated yield after
column chromatography, epimers differ at this carbon atom, dr= diastereomeric ratio.
3. Conclusion
The modulation of traditional carbon-Ferrier rearrangement reaction was done by altering it to
one pot Mukaiyama type carbon Ferrier rearrangement reaction avoiding hazardous strong bases.
The carbon-Ferrier reaction was accomplished on unactivated aryl methyl ketones
(acetophenones) to form different substituted pyranosides. The method was applied to the

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chroman systems for the construction of some biologically active chroman C-glycosides. All the
synthesized compounds are being evaluated for biological activities, results of which will be
disclosed in due course.
4. Experimental
4.1. General information
Reactions were carried out under an atmosphere of nitrogen with a septum cap in oven-dried
glassware with magnetic stirring. Anhydrous CH2Cl2 was purified by passage through a bed of
activated alumina. Analytical thin-layer chromatography was performed using silica gel plates.
Visualization was accomplished with UV light. 1H NMR spectra were recorded with a 500 MHz
spectrometer or 300 MHz spectrometer, and are reported in ppm using solvent as an internal
standard (CDCl3 at δ = 7.28 ppm). Data are reported as [ap = apparent, s = singlet, d = doublet, t
= triplet, q = quartet, m = multiplet, br= broad; coupling constant(s) in Hz; integration]. Proton-
decoupled 13C NMR spectra were recorded with a 125 MHz spectrometer or 75 MHz
spectrometer, and are reported in ppm using solvent as an internal standard (CDCl3 at δ = 77.0
ppm). Melting points were determined using a capillary melting point apparatus. The products
were purified by column chromatography on silica gel (60-120/100-200/230-400 mesh) using
petroleum ether–ethyl acetate as the eluent to obtain the pure products. Reagents used were
mostly purchased from Sigma Aldrich if not mentioned otherwise.
(I) General information for the synthesis of glucopyranoside.
To an oven-dried 10-mL round-bottomed flask under N2 was added CH2Cl2 (5.0 mL),
Acetophenone/chromanone (1.0 mmol, 200 mg), iPr2NEt (234 µL, 1.20 mmol), TBSOTf (324
ꢀL 1.25 mmol). After 20 min, protected sugar (1.1 mmol. 335 mg) was added at 0°C, and the
mixture was stirred at room temperature for the indicated time. The reaction mixture was passed
through a silica gel plug (1cm×5 cm) with Et2O and was neutralized by aqueous NaHCO3
solution. The Et2O extract was removed by rotary evaporation. The product was purified by
silica gel chromatography (10 to 15% EtOAc/ hexanes) from which only the major product was
isolated. The spectral data of representative compounds are shown below.
(II) General information for the synthesis of 4-hydroxy coumarin-3C glycoside (1i)

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To an oven-dried 10-mL round-bottomed flask under N2 was added CH2Cll2 (5.0 mL) 4-hydroxy
coumarin (1.0 mmol, 200 mg), TBSOTf (48 ꢀL 0.2mmol). After 20 min, protected sugar (1.1
mmol. 368 mg) was added at 0°C, and the mixture was stirred at room temperature for the
indicated time. The reaction mixture was passed through a silica gel plug (1cm×5 cm) with Et2O
and was neutralized by aqueous NaHCO3 solution. The Et2O extract was removed by rotary
evaporation. The product was purified by silica gel chromatography (10 to 15% EtOAc/ hexanes)
and the major product was isolated. The spectral data of representative compounds are shown
below.
4.2 Spectral Data:
4.2.1. 1-((4, 6-Di-O-acetyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-1-phenylethanone
(1a)
Prepared by the general procedure (I) using acetophenone (200 mg, 1.66 mmol.) iPr2NEt (348
µL, 1.99 mmol), TBSOTf (479 ꢀL 2.07 mmol). Glucal triacetate (1.82 mmol. 498 mg) to obtain
1a in 66 % (350 mg) yield, Colorless liquid, Rf = 0.5 (petroleum ether/ethyl acetate = 90:10)
1H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 7.5 Hz, 2H), 7.52 (t, J = 7.4 Hz, 1H), 7.42 (d, J = 7.7
Hz, 2H), 6.01 (d, J = 10.3 Hz, 1H), 5.83 – 5.72 (m, 1H), 5.07 (s, 1H), 4.87 (d, J = 1.9 Hz, 1H),
4.17 (dd, J = 11.9, 6.6 Hz, 1H), 4.06 (dd, J = 11.9, 3.6 Hz, 1H), 3.92 (td, J = 6.3, 3.7 Hz, 1H),
3.40 (dd, J = 16.3, 7.1 Hz, 1H), 3.08 (dd, J = 16.3, 6.5 Hz, 1H), 2.02 (s, 3H), 1.95 (s, 3H).
[M+H]+; HRMS: Found m/z 332.1259 calcd. For C18H20O6 (332.1260).
4.2.2.
1-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-1-(4-
methylyphenyl)-ethanone (1b)
Prepared by the general procedure (I) using 4’-methyl acetophenone (200 mg, 1.49 mmol.)
iPr2NEt (311 µL, 1.78 mmol), TBSOTf (427 ꢀL 1.86 mmol). Glucal triacetate (1.63 mmol. 446
mg) to obtain 1b in 55 % (280 mg) yield, colourless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 89:11),
1H NMR (400 MHz, CDCl3) 7.85 – 7.59 (m, 2H), 7.65 – 7.43 (m, 2H), 6.00 (ddd, J = 10.4, 2.4,
1.5 Hz, 1H), 5.83 – 5.69 (m, 1H), 5.08 (dd, J = 3.0, 1.5 Hz, 1H), 4.85 (m, 1H), 4.18 (dd, J = 11.9,

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6.5 Hz, 1H), 4.06 (dd, J = 11.9, 3.6 Hz, 1H), 3.92 (td, J = 6.3, 3.7 Hz, 1H), 3.50 – 3.30 (m, 1H),
3.06 (m, 1H), 2.35 (s, 3H), 2.02 (s, 3H), 1.96 (s, 3H).
[M+H]+; HRMS: Found m/z 346.1414 calcd. For C19H22O6 (346.1416).
4.2.3.
1-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-1-(3-
methylyphenyl)-ethanone (1c)
Prepared by the general procedure (I) using 3’-methylacetophenone (200 mg, 1.49 mmol.)
iPr2NEt (311 µL, 1.78 mmol), TBSOTf (427 ꢀL 1.86 mmol). Glucal triacetate (1.63 mmol. 446
mg) to obtain 1c in 56 % (288 mg) yield, colourless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 89:11),
1H NMR (400 MHz, CDCl3) 7.68 (d, J = 10.9 Hz, 2H), 7.30 (dt, J = 14.8, 7.5 Hz, 2H), 6.01 (ddd,
J = 10.4, 2.4, 1.5 Hz, 1H), 5.86 – 5.69 (m, 1H), 5.05 (dd, J = 3.0, 1.5 Hz, 1H), 4.95 – 4.72 (m,
1H), 4.17 (dd, J = 11.9, 6.5 Hz, 1H), 4.08 (dd, J = 11.9, 3.6 Hz, 1H), 3.91 (d, J = 3.6 Hz, 1H),
3.39 (m,1H), 3.05 (m, 1H), 2.36 (s, 3H), 2.01 (s, 3H), 1.96 (s, 3H).
[M+H]+; HRMS: Found m/z 346.1415 calcd. For C19H22O6 (346.1416).
4.2.4.
1-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-1-(3-
fluorophenyl)-ethanone (1d)
Prepared by the general procedure (I) using4’-fluoroacetophenone (200 mg, 1.44 mmol.)
iPr2NEt (300 µL, 1.72 mmol), TBSOTf (360 ꢀL 1.80 mmol). Glucal triacetate (1.59 mmol. 432
mg) to obtain 1d in 67 % (338 mg) yield, colourless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 90:10).
1H NMR (400 MHz, CDCl3) δ 7.78 – 7.68 (m, 2H), 7.55 (d, J = 8.6 Hz, 2H), 5.98 (ddd, J = 10.4,
2.4, 1.5 Hz, 1H), 5.78 (ddd, J = 10.4, 3.0, 2.1 Hz, 1H), 5.06 (ddd, J = 6.9, 3.3, 2.0 Hz, 1H), 4.83
(ddd, J = 8.8, 4.6, 2.2 Hz, 1H), 4.17 (dd, J = 11.9, 6.7 Hz, 1H), 4.06 – 4.01 (m, 1H), 3.91 (td, J =
6.3, 3.8 Hz, 1H), 3.35 (m, 1H), 3.05 – 2.99 (m, 1H), 2.01 (s, 3H), 1.96 (s, 3H).
[M+H]+; HRMS: Found m/z 350.1163 calcd. For C18H19FO6 (350.1166).
4.2.5.
1-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-1-(3-
bromophenyl)-ethanone (1e)

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Prepared by the general procedure (I) using 4’-bromoacetophenone (200 mg, 1.00 mmol.)
iPr2NEt (209 µL, 1.20 mmol), TBSOTf (287 ꢀL 1.25 mmol). Glucal triacetate (1.11 mmol. 279
mg) to obtain 1e in 68 % (278 mg) yield, colourless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 92:08).
1H NMR (400 MHz, CDCl3) δ 7.75 (d, J = 8.6 Hz, 2H), 7.55 (d, J = 8.6 Hz, 2H), 5.97 (d, J = 0.8
Hz, 1H), 5.80 (s, 1H), 5.06 (ddd, J = 6.9, 3.3, 2.0 Hz, 1H), 4.83 (ddd, J = 8.8, 4.6, 2.2 Hz, 1H),
4.17 (dd, J = 11.9, 6.7 Hz, 1H), 4.05 (dd, J = 11.9, 3.7 Hz, 1H), 3.91 (td, J = 6.3, 3.8 Hz, 1H),
3.36 (m, 1H), 3.03 (m, 1H), 2.04 – 1.93 (m, 6H).
[M+H]+; HRMS: Found m/z 410.0363 calcd. For C18H19BrO6 (410.0365).
4.2.6.
1-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-1-(3,4-(2,2-
dimethyl-1,3-dioxolo)phenyl)-ethanone (1f)
Prepared by the general procedure (I) using 3’,4’-methylenedioxyacetophenone (200 mg, 1.21
mmol.) iPr2NEt (255 µL, 1.46 mmol), TBSOTf (347 ꢀL 1.51 mmol). Glucal triacetate (1.33
mmol. 362 mg) to obtain 1f in 60 % (273 mg) yield, colourless liquid, Rf = 0.5 (petroleum
ether/ethyl acetate = 90:10),
1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 8.2 Hz, 1H), 7.36 (s, 1H), 6.78 (d, J = 8.2 Hz, 1H),
5.94 (d, J = 26.9 Hz, 2H), 5.90 (d, J = 10.3 Hz, 1H), 5.68 (d, J = 10.3 Hz, 1H), 5.22 (d, J = 10.8
Hz, 1H), 4.75 (s, 1H), 3.94 (td, J = 6.3, 3.8 Hz, 1H), 3.80 – 3.59 (m, 1H), 3.29 – 3.17 (m, 1H),
2.92 (dd, J = 16.6, 7.4 Hz, 1H), 2.08 – 1.91 (m, 6H).
[M+H]+; HRMS: Found m/z 376.1155 calcd. For C19H20O8 (376.1158).
4.2.7. 1-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl)-1-phenylethanone
(2a)
Prepared by the general procedure (I) using acetophenone (200 mg, 1.66 mmol.) iPr2NEt (348
µL, 1.99 mmol), TBSOTf (479 ꢀL 2.07 mmol). Galactal triacetate (1.82 mmol. 498 mg) to
obtain 2agin 69 % (347 mg) yield, colorless liquid, Rf = 0.5 (petroleum ether/ethyl acetate =
90:10),

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1H NMR (400 MHz, CDCl3) δ 8.02 – 7.73 (m, 2H), 7.52 (t, J = 7.4 Hz, 1H), 7.42 (t, J = 7.6 Hz,
2H), 6.11 (dd, J = 10.3, 3.0 Hz, 1H), 5.96 (ddd, J = 10.2, 5.1, 2.1 Hz, 1H), 5.09 – 4.98 (m, 1H),
4.96 (t, J = 6.9 Hz, 1H), 4.22 – 4.03 (m, 3H), 3.51 – 3.33 (m, 1H), 3.11 – 2.91 (m, 1H), 2.01 (s,
3H), 1.91 (s, 3H).
[M+H]+; HRMS: Found m/z 332.1259 calcd. For C18H20O6 (332.1260).
4.2.8. 1-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl)-1-(3-methylphenyl)-
ethanone (2b)
Prepared by the general procedure (I) using 3’-methylacetophenone (200 mg, 1.49 mmol.)
iPr2NEt (311 µL, 1.78 mmol), TBSOTf (427 ꢀL 1.86 mmol). Galactal triacetate (1.63 mmol. 446
mg) to obtain 2b in 60 % (309 mg) yield, colourless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 89:11),
1H NMR (400 MHz, CDCl3) δ 7.67 (d, J = 9.3 Hz, 2H), 7.40 – 7.25 (m, 2H), 6.10 (dd, J = 10.3,
3.0 Hz, 1H), 5.95 (ddd, J = 10.2, 5.2, 2.1 Hz, 1H), 5.04 (d, J = 4.7 Hz, 1H), 5.00 – 4.83 (m, 1H),
4.20 – 3.97 (m, 3H), 3.46 – 3.22 (m, 1H), 3.03 (dd, J = 16.1, 6.6 Hz, 1H), 2.34 (d, J = 3.9 Hz,
3H), 2.01 (s, 3H), 1.91 (s, 3H).
[M+H]+; HRMS: Found m/z 346.1414 calcd. For C19H22O6 (346.1416).
4.2.9. 1-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl)-1-(4-fluorophenyl)-
ethanone (2c)
Prepared by the general procedure (I) using4’-fluoroacetophenone (200 mg, 1.44 mmol.)
iPr2NEt (300 µL, 1.72 mmol), TBSOTf (360 ꢀL 1.80 mmol). Galactal triacetate (1.59 mmol. 432
mg) to obtain 2c in 66 % (332 mg) yield, colourless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 90:10),
1H NMR (400 MHz, CDCl3) δ 7.99 – 7.82 (m, 2H), 7.09 (td, J = 8.6, 1.9 Hz, 2H), 6.09 (m, 1H),
6.00 – 5.84 (m, 1H), 5.05 (d, J = 5.0 Hz, 1H), 4.94 (s, 1H), 4.13 (m, 3H), 3.39 – 3.29 (m, 1H),
3.01 (m, 1H), 2.01 (s, 3H), 1.91 (s, 3H).
[M+H]+; HRMS: Found m/z 350.1165 calcd. For C18H19FO6 (350.1166).

ACCEPTED MANUSCRIPT
4.2.10. 1-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl)-1-(3-bromophenyl)-
ethanone(2d)
Prepared by the general procedure (I) using 3’-bromoacetophenone (200 mg, 1.00 mmol.)
iPr2NEt (209 µL, 1.20 mmol), TBSOTf (287 ꢀL 1.25 mmol). Galactal triacetate (1.11 mmol. 279
mg) to obtain 2d in 69 % (282 mg) yield, colourless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 93:07),
1H NMR (400 MHz, CDCl3) δ 7.75 (d, J = 8.4 Hz, 2H), 7.56 (d, J = 8.4 Hz, 2H), 6.22 – 5.99 (m,
1H), 5.96 (ddd, J = 10.2, 5.0, 1.8 Hz, 1H), 5.03 (t, J = 5.8 Hz, 1H), 4.93 (t, J = 6.6 Hz, 1H), 4.16
– 3.97 (m, 3H), 3.33 (m, 1H), 3.12 – 2.92 (m, 1H), 2.01 (s, 3H), 1.92 (s, 3H).
[M+H]+; HRMS: Found m/z 410.0361 calcd. For C18H19BrO6 (410.0365).
4.2.11.
1-((4-O-acetyloxy-5-methyl)-2,3,6-trideoxy-α-L-erythro-hex-2-enopyranosyl)-1-
phenylethanone (3a)
Prepared by the general procedure (I) using acetophenone (200 mg, 1.66 mmol.) iPr2NEt (348
µL, 1.99 mmol), TBSOTf (479 ꢀL 2.07 mmol). Rhamnal diacetate (1.82 mmol. 389 mg) to
obtain 3a in 49 % (223 mg) yield, Whitish, colourless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 90:10),
1H NMR (400 MHz, CDCl3) δ 8.10 – 7.83 (m, 2H), 7.66 – 7.54 (m, 1H), 7.49 (t, J = 7.6 Hz, 2H),
6.08 (ddd, J = 10.3, 2.1, 1.2 Hz, 1H), 5.85 (ddd, J = 10.4, 3.5, 2.0 Hz, 1H), 5.02 – 4.82 (m, 2H),
4.03 – 3.84 (m, 1H), 3.47 (m, 1H), 3.16 (dd, J = 16.5, 6.7 Hz, 1H), 2.10 (d, J = 3.5 Hz, 3H), 1.27
(d, J = 6.6 Hz, 3H). [M+H]+; HRMS: Found m/z 274.1203 calcd. For C16H18O4 (274.1205).
4.2.12. 1-((4-O-acetyloxy-5-methyl)-2,3,6-trideoxy-α-L-erythro-hex-2-enopyranosyl)-1-(3-
chlorophenyl)-ethanone (3b)
Prepared by the general procedure (I) using 3’-chloroacetophenone (200 mg, 1.49 mmol.)
iPr2NEt (310 µL, 1.78 mmol), TBSOTf (427 ꢀL 1.86 mmol). Rhamnal diacetate (1.63 mmol.
348 mg) to obtain 3b in 53 % (227 mg) yield, colourless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 93:7).

ACCEPTED MANUSCRIPT
1H NMR (400 MHz, CDCl3) δ 7.85 – 7.65 (m, 2H), 7.38 (dt, J = 14.8, 7.5 Hz, 2H), 6.07 (ddd, J
= 10.3, 2.1, 1.3 Hz, 1H), 5.84 (ddd, J = 10.4, 3.5, 2.1 Hz, 1H), 5.03 – 4.66 (m, 2H), 4.01 – 3.84
(m, 1H), 3.58 – 3.25 (m, 1H), 3.14 (dd, J = 16.5, 6.7 Hz, 1H), 2.43 (s, 3H), 2.10 (d, J = 3.7 Hz,
3H), 1.34 – 1.11 (m, 3H).
[M+H]+; HRMS: Found m/z 288.1360 calcd. For C17H20O4 (288.1362).
4.2.13. 1-((4-O-acetyloxy-5-methyl)-2,3,6-trideoxy-α-L-erythro-hex-2-enopyranosyl)-1-(4-
fluorophenyl)-ethanone (3c)
Prepared by the general procedure (I) using4’-fluoroacetophenone (200 mg, 1.44 mmol.)
iPr2NEt (300 µL, 1.72 mmol), TBSOTf (360 ꢀL 1.80 mmol). Rhamnal diiacetate (1.59 mmol.
342 mg) to obtain 3c in 59 % (248 mg) yield, colourless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 90:10),
1H NMR (400 MHz, CDCl3) δ 8.00 (m, 2H), 7.25 – 6.95 (m, 2H), 6.10 – 5.99 (m, 1H), 5.84
(ddd, J = 10.3, 3.4, 2.0 Hz, 1H), 4.97 – 4.78 (m, 2H), 4.03 – 3.82 (m, 1H), 3.41 (m, 1H), 3.10 (m,
1H), 2.09 (d, J = 2.7 Hz, 3H), 1.24 (t, J = 11.3 Hz, 3H).
[M+H]+; HRMS: Found m/z 292.1109 calcd. For C16H17FO4 (292.1111).
4.2.14. 1-((4-O-acetyloxy-5-methyl)-2,3,6-trideoxy-α-L-erythro-hex-2-enopyranosyl)-1-(3-
bromophenyl)-ethanone (3d)
Prepared by the general procedure (I) using 3’-bromoacetophenone (200 mg, 1.00 mmol.)
iPr2NEt (209 µL, 1.20 mmol), TBSOTf (287 ꢀL 1.25 mmol). Rhamnal diacetate (1.11 mmol.
238 mg) to obtain 3d in 62 % (254 mg) yield, colourless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 92:08),
1H NMR (400 MHz, CDCl3) δ 7.91 – 7.60 (m, 2H), 7.60 – 7.46 (m, 2H), 5.97 (ddd, J = 10.3, 2.1,
1.2 Hz, 1H), 5.77 (ddd, J = 10.3, 3.6, 2.0 Hz, 1H), 4.96 – 4.66 (m, 2H), 3.86 (dd, J = 6.5, 4.5 Hz,
1H), 3.58 – 3.15 (m, 1H), 3.02 (dd, J = 16.4, 6.4 Hz, 1H), 2.02 (s, 3H), 1.18 (d, J = 6.6 Hz, 3H).
[M+H]+; HRMS: Found m/z 352.0308 calcd. For C16H17BrO4 (352.0310).

ACCEPTED MANUSCRIPT
4.2.15. 3-((4,6-Di-O-acetyl)-2,3-dideoxy-α-
chromanone (1g)
D-erythro-hex-2-enopyranosyl)-2,2-dimethyl-4-
Prepared by the general procedure (I) using 2,2-dimethylchroman-4-one (200 mg, 1.13 mmol.)
iPr2NEt (237 µL, 1.36mmol), TBSOTf (324 ꢀL 1.41 mmol), Glucaltriacetate (1.25 mmol., 340
mg) to obtain 1g in 66 % (291 mg) yield, (dr =4:1), major isomer isolated (53%= 233 mg).
colourless liquid, Rf = 0.5 (petroleum ether/ethyl acetate = 88:12),
1H NMR (400 MHz, CDCl3) δ 7.82 (dd, J = 7.8, 1.6 Hz, 1H), 7.56 – 7.33 (m, 1H), 7.04 – 6.77
(m, 2H), 6.10 – 5.97 (m, 1H), 5.95 – 5.80 (m, 1H), 5.05 (dd, J = 3.6, 2.0 Hz, 1H), 4.77 (dd, J =
5.4, 2.4 Hz, 1H), 4.14 (dd, J = 11.7, 5.5 Hz, 1H), 3.86 (ddd, J = 9.3, 8.8, 3.5 Hz, 2H), 2.77 (d, J =
5.6 Hz, 1H), 2.06 (s, 3H), 2.03 (s, 3H) 1.56 (s, 3H), 1.44 (s, 3H).
13CNMR (126MHz, CDCl3) δ190.4, 69.5, 168.1, 157.5, 134.1, 129.9, 124.6, 122.0, 119.0, 119.0,
116.5, 78.2, 69.1, 67.3, 62.3, 60.4, 56.8, 24.1, 23.8, 19.3, 19.1.
[M+H]+; HRMS: Found m/z 388.1520 calcd. For C21H24O7 (388.1522).
4.2.16.
3-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl)-2,2-dimethyl-4-
chromanone (2e)
Prepared by the general procedure (I) using 2,2-dimethylchroman-4-one (200 mg, 1.13 mmol.)
iPr2NEt (237 µL, 1.36mmol), TBSOTf (324 ꢀL 1.41 mmol), Galactaltriacetate (1.25 mmol., 340
mg) to obtain 2e in 68 % (300 mg) yield, (dr =3:1), major isomer isolated (51 %= 225 mg).
colourless liquid, Rf = 0.5 (petroleum ether/ethyl acetate = 89:11),
1H NMR (400 MHz, CDCl3) δ 7.72 (dd, J = 7.8, 1.4 Hz, 1H), 7.46 – 7.31 (m, 1H), 6.89 (m, 2H),
5.90 (ddd, J = 10.2, 5.3, 2.2 Hz, 1H), 5.53 (dd, J = 10.3, 3.1 Hz, 1H), 5.07 – 4.89 (m, 1H), 4.71
(dd, J = 4.6, 2.8 Hz, 1H), 4.13 (m, 2H), 2.63 (d, J = 7.6 Hz, 1H), 2.06 (s, 3H), 2.03 (s, 3H),1.58
(s, 3H), 1.33 (s, 3H).
13C NMR (126 MHz, CDCl3) δ 193.0, 170.2, 170.3, 158.8, 136.7, 132.4, 126.8, 123.5, 120.7,
120.0, 117.8, 81.2, 69.3, 68.3, 63.0, 62.6, 57.0, 29.8, 25.9, 25.6, 20.6.
[M+H]+; HRMS: Found m/z 388.1519 calcd. For C21H24O7 (388.1522).

ACCEPTED MANUSCRIPT
4.2.17.
3-((4-O-acetyl-5-methyl)-2,3,6-trideoxy-α-L-erythro-hex-2-enopyranosyl)-2,2-
dimethyl-4-chromanone (3e)
Prepared by the general procedure (I) using 2,2-dimethylchroman-4-one (200 mg, 1.13 mmol.)
iPr2NEt (237 µL, 1.36mmol), TBSOTf (324 ꢀL 1.41 mmol), rhamnal diacetate (1.25 mmol., 267
mg) to obtain 3e in 67 % (255 mg) yield, (dr=1:4), major isomer isolated (53.5 %= 204 mg).
colourless liquid, Rf = 0.5 (petroleum ether/ethyl acetate = 90:10),
1H NMR (400 MHz, CDCl3) δ 7.82 – 7.66 (m, 1H), 7.45 – 7.33 (m, 1H), 7.02 – 6.75 (m, 2H),
5.86 – 5.43 (m, 2H), 4.99 – 4.57 (m, 2H), 3.80 (m, 1H), 3.47 (dd, J = 8.7, 6.2 Hz, 1H), 2.67 (d, J
= 6.6 Hz, 1H), 2.00 (d, J = 6.5 Hz, 3H), 1.18 (s, 9H).
13C NMR (126 MHz, CDCl3) δ 192.0, 170.7, 158.9, 136.0, 131.4, 126.7, 124.7, 120.9, 120.5,
118.2, 81.5, 73.1, 72.7, 67.4, 58.7, 25.7, 24.5, 18.3, 16.9.
[M+H]+; HRMS: Found m/z 330.1465 calcd. For C19H22O5 (330.1467).
4.2.18. 3-((4,6-Di-benzoyloxy)-2,3-dideoxy-α-D-threo-hex-2-enopyranosyl)-2,2-dimethyl-4-
chromanone (4a)
Prepared by the general procedure (I) using 2,2-dimethylchroman-4-one (200 mg, 1.13 mmol.)
iPr2NEt (237 µL, 1.36mmol), TBSOTf (324 ꢀL 1.41 mmol), Galactaltribenzoate (1.25 mmol.,
573 mg) to obtain 4a in 55 % (320 mg) yield, (dr=3:1), major isomer isolated (41.2 %= 240 mg).
colourless liquid, Rf = 0.5 (petroleum ether/ethyl acetate = 87:13),
1H NMR (400 MHz, CDCl3) δ 8.03 (t, J = 7.4 Hz, 4H), 7.82 (dd, J = 7.8, 1.3 Hz, 1H), 7.48 (m ,
7H), 7.10 – 6.88 (m, 2H), 6.13 (ddd, J = 10.2, 5.2, 2.2 Hz, 1H), 5.67 (dd, J = 10.3, 3.2 Hz, 1H),
5.44 (dd, J = 5.0, 1.8 Hz, 1H), 4.99 – 4.82 (m, 1H), 4.67 (dd, J = 10.9, 6.8 Hz, 1H), 4.56 – 4.42
(m, 2H), 2.75 (d, J = 7.4 Hz, 1H), 1.63 (s, 3H), 1.37 (s, 3H).
13C NMR (126 MHz, CDCl3) δ 193.0, 166.1, 165.9, 159.2, 136.5, 133.2, 133.1, 132.6, 129.7,
129.6. 129.6, 128.4, 126.6, 123.2, 121.0, 120.2, 118.2, 81.0, 69.4, 69.0, 64.1, 63.3, 57.6, 26.2,
25.3.
[M+H]+; HRMS: Found m/z 512.1833 calcd. For C31H28O7 (512.1835).

ACCEPTED MANUSCRIPT
4.2.19. 6-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)-7-methoxy-2,2-
dimethyl-4-chromanone (1h)
Prepared by the general procedure (I) using 7-methoxy-2,2-dimethylchroman-4-one (200 mg,
0.97mmol.) iPr2NEt (202 µL, 1.16mmol), TBSOTf (278 ꢀL 1.21 mmol), Glucaltriacetate (1.06
mmol., 291 mg) to obtain 1h in 70 % (284 mg). Colorless liquid, Rf = 0.5 (petroleum ether/ethyl
acetate = 90:10),
1H NMR (400 MHz, CDCl3) δ 7.79 (s, 1H), 6.30 (s, 1H), 5.81 (dt, J = 10.3, 1.6 Hz, 1H), 5.76 –
5.63 (m, 1H), 5.45 (d, J = 1.5 Hz, 1H), 5.38 – 5.26 (m, 1H), 4.25 (m, 1H), 4.13 (m, 1H), 3.98 (m,
1H), 3.87 – 3.70 (m, 3H), 2.58 (s, 2H), 2.03 (d, J = 3.3 Hz, 6H), 1.37 (d, J = 3.9 Hz, 6H).
13C NMR (126 MHz, CDCl3) δ 190.8, 171.0, 170.2, 162.8, 161.7, 131.9, 126.5, 124.7, 122.2,
113.7, 99.3, 79.7. 74.9, 70.8, 65.2, 63.5, 55.8, 48.4, 26.6, 26.5, 21.0, 20.8.
[M+H]+; HRMS: Found m/z 418.1626 calcd. For C22H26O8 (418.1628).
4.2.20. 3-((4,6-Di-O-acetyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)coumarin (1i)
Prepared by the general procedure (II) using 4-hydroxy-2H-chromen-2-one (200 mg, 0.81
mmol.), TBSOTf (37 ꢀL 0.2 mmol), Glucaltriacetate (0.89 mmol., 243 mg) to obtain 1i in 68 %
(206 mg) yield, (dr =4:1), major isomer isolated (68 %= 165 mg). colourless liquid, Rf = 0.5
(petroleum ether/ethyl acetate = 65:35),
1H NMR (400 MHz, CDCl3) δ 10.00 (s, 1H), 7.89 (dd, J = 8.2, 1.5 Hz, 1H), 7.68 – 7.37 (m, 1H),
7.29 ( m, 2H), 6.02 – 5.85 (m, 1H), 5.40 – 5.16 (m, 1H), 4.94 (dd, J = 10.4, 2.7 Hz, 1H), 4.50 –
4.29 (m, 2H), 4.29 – 4.12 (m, 2H), 2.15 (d, J = 2.7 Hz, 6H).
13C NMR (126 MHz, CDCl3) δ 170.8, 170.0, 162.4, 161.5, 152.9, 132.2, 123.9, 123.3, 116.4,
116.1, 101.9, 73.5, 72.6, 72.4, 69.0, 62.2, 57.4, 20.9, 20.7.
[M+H]+; HRMS: Found m/z 374.1000 calcd. For C19H18O8 (374.1002).
Acknowledgements
Authors are thankful to CSIR-IIIM (MLP4015, BSC0108) for generous funding. IIIM no.:
IIIM/1974/2016
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Highlights:
ꢀ Use of TBSOTf for highly stereoselective C-glycosylation
ꢀ Syntheses of chromanone-3-C-glycosides