Palladium(0)-catalysed synthesis of 2,3- and 3,4-unsaturated aryl β-O-glycosides

Article abstract of DOI:10.1016/j.carres.2015.08.016

Arylation of 6-O-tert-butyldiphenylsilyl-3,4-di-O-isobutyloxycarbonyl-d-glucal (3) with various phenols in the presence of a catalytic amount of palladium(0) gave the corresponding 2,3- and 3,4-unsaturated β-O-glycosides. The reaction is stereospecific, i

Full text of DOI:10.1016/j.carres.2015.08.016

Carbohydrate Research 417 (2015) 34–40
Contents lists available at ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Palladium(0)-catalysed synthesis of 2,3- and 3,4-unsaturated aryl
β-O-glycosides
Agnieszka Kubiak, Robert Kołodziuk, Stanisław Porwan´ ski, Anna Zawisza *
Department of Organic and Applied Chemistry, University of Łód´z, Tamka 12, 91-403 Łód´z, Poland
A R T I C L E
I N F O
A B S T R A C T
Article history:
Received 28 July 2015
Received in revised form 26 August 2015
Accepted 28 August 2015
Available online 5 September 2015
Arylation of 6-O-tert-butyldiphenylsilyl-3,4-di-O-isobutyloxycarbonyl-d-glucal (3) with various phenols
in the presence of a catalytic amount of palladium(0) gave the corresponding 2,3- and 3,4-unsaturated
β-O-glycosides. The reaction is stereospecific, in all cases, only the β-anomer is formed.
© 2015 Elsevier Ltd. All rights reserved.
Keywords:
d-Glucal
O-Glycosides
Ferrier rearrangement
Allylic alkylation reaction
Homogeneous catalysis
Palladium
Aryl and alkyl 2,3-unsaturated glycosides are useful chiral in-
termediates in the synthesis of several biologically active natural
products.1–3
The direct and straightforward method for the synthesis of 2,3-
unsaturated O-glycosides is the acid-catalysed allylic rearrangement
of glycals in the presence of alcohols, the first reported by Ferrier
et al. in 1962.4,5 This reaction is now currently known as Ferrier
rearrangement,6 or the Ferrier (I) reaction.7 A variety of reagents are
reported to promote this transformation which include Lewis and
Brønsted acids as well as oxidants.8–10
with NaI and Zn—Cu-couple,19 and palladium–indium bromide-
mediated carbonyl allylation20 or by alkylation of ethyl α-O-Δ2-
glycosides, having a leaving group at C-4 in the presence of
Pd(0)-complex.21
Following our continuing interest in the formation of a carbon–
oxygen bond catalysed by palladium(0) complexes22 and particularly
the use of this very mild methodology in carbohydrate chemistry,21
we report in this paper the use of 6-O-tert-butyldiphenylsilyl-3,4-
di-O-isobutyloxycarbonyl-d-glucal in the synthesis of 2,3- and 3,4-
unsaturated O-glycosides.
Several research groups have focused their attention on the use
of transition-metal catalysts for the activation of appropriately C-3
functionalised glucal derivatives.5,11 Developments in this area have
been associated particularly with the use of palladium5,12 and gold
catalysts.5,13 The transition metal-catalysed Ferrier-type glycosylation
reactions customarily proceed with excellent stereocontrol. In ad-
dition, to being a catalytic reaction, the reaction has the added
advantage that it can be accomplished under quite mild condi-
tions without the stoichiometric use of strong Lewis acid promoters.
In turn, 3,4-unsaturated O-glycosides have been synthesised
via a Luche reduction of the sugar enones,14 by Claisen15 or Overman16
rearrangement of 2,3-unsaturated carbohydrates, by reduction 2,3-
unsaturated glycosides,17 via removal of vicinal diol by treatment
In our study, we expected that the reaction of phenols on a π-allyl
palladium complex obtained by reacting palladium(0) with an un-
saturated carbohydrate possessing a good leaving group at the allylic
position could lead to the formation of an unsaturated O-glycosides.
We choose for our study the 1,2-unsaturated carbohydrate 3 easily
prepared from d-glucal according to Scheme 1.
Commercially available d-glucal 1 was first treated with tert-
butyldiphenylsilylchloride in dichloromethane to yield monosilyl-
protected derivative 2a in 59% yield and 3,6-disilylated sugar 2b in
28% yield.23 Condensation of 2a with isobutyl chloroformate at 0 °C
afforded dicarbonate 3 in 86% yield.
Initial experiment was performed with dicarbonate 3 as the donor
and 2,5-dimethylphenol 4a as the acceptor (Scheme 2, Table 1).
The reaction performed in tetrahydrofuran at room tem-
18
with PPh3 and CHI3 or by reaction 3,4-dimesylate derivatives
perature in the presence of
a catalytic amount of tris
(dibenzylideneacetone)dipalladium and 1,4-bis(diphenylphosphine)
butane gave 2,3-unsaturated O-glycoside 5a and 3,4-unsaturated
isomer 6a in 20% and 1% yields, respectively (Table 1, entry 1). In-
creasing the temperature to 60 °C afforded the product 5a in
*
Corresponding author. Department of Organic and Applied Chemistry, University
of Łódz´, Tamka 12, 91-403 Łódz´, Poland. Tel.: +48 42 6355802; fax: +48 42 6655162.
E-mail address: azawisza@chemia.uni.lodz.pl (A. Zawisza).
http://dx.doi.org/10.1016/j.carres.2015.08.016
0008-6215/© 2015 Elsevier Ltd. All rights reserved.

A. Kubiak et al./Carbohydrate Research 417 (2015) 34–40
35
Scheme 1. Synthesis of unsaturated carbohydrate 3.
an improved yield of 56% and 6a of 22% after 24 hours (Table 1,
entry 2).
β-anomer in Ferrier rearrangement is the very challenging task. To
the best of our knowledge, there are only three published methods
for synthesis of 2,3-unsaturated-β-glycosides.25
O-Arylation reaction of 3,4-di-O-isobutyloxycarbonyl-d-glucal 3
we also carried out with other nucleophiles. Taking into account
the results obtained for 4a, reactions with phenols 4b–j were per-
formed in THF in the presence of dppb as a ligand at 60 °C. dppe
gave similar results, even better selectivity in favor of the 2,3-
unsaturated isomer 5a, but for economic reasons we have chosen
dppb for further study.
Reaction with dppe as the ligand afforded 5a in a good yield of
74% and isomer 6a in 6% yield after 24 h (Table 1, entry 3). When
PPh3 was used, a mixture of the 2,3-unsaturated carbohydrate 5a
and its 3,4-unsaturated isomer 6a was obtained with 24% yield in
both cases (Table 1, entry 4). We also investigated the effect of the
solvent on this O-glycosylation reaction (Table 1, entries 5–6). In
CH3CN, products 5a and 6a were obtained in 44% and 6% yields re-
spectively. The use of CH2Cl2 provided good yields: 5a-46% and
6a-24%.
The reaction of unsaturated carbohydrate
3 with 2,3-
The structures of these two compounds were assigned through
their 1H and 13C NMR data. The main characteristic differences
between 5a and 6a are the chemical shifts of H-4 and C-4 at δ
4.99 ppm and 68.1 ppm respectively for 5a, and H-2 and C-2 at δ
4.90 ppm and 73.0 ppm, respectively for compound 6a. The ob-
served downfield shift for C-1 in compound 6a (δ = 99.3 ppm) is also
characteristic for 3,4-unsaturation (Table 2).24
Most importantly, the reaction is stereospecific, and only the
β-anomer was formed. The β anomeric configuration was readily
derived from the 1H NMR and the literature data with the signal
of H-1 corresponding to the β anomer (δ 5.82 ppm for 5a) being
at lower field than the signal of the α anomer (δ 5.69 ppm).8a It
should be noted that due to the anomeric effect obtaining the
dimethylphenol (4b) gave the 2,3-unsaturated O-glycoside 6b in 47%
yield and 3,4-unsaturated isomer 6b in 16% yield (Table 3, entry 2).
Characteristic differences in the chemical shift values of isomers 5b
and 6b are given in Table 2.
When 2,4-dimethylphenol (4c) was used as the nucleophile in
this reaction, the corresponding O-glycosides 5c and 6c were ob-
tained in 49% and 11% yields, respectively (Table 3, entry 3).
The reaction with 3,5-dimethylphenol (4d) gave similar results
as for 2,5-dimethylphenol (4a). As the major product was isolated
Table 2
Selected 1H and 13C NMR data for compounds 5a–j and 6a–ja
Table 1
Phenol
2,3-Unsaturated isomer 5
3,4-Unsaturated isomer 6
Effect of ligand and solvent on Pd0-catalysed O-arylation reaction unsaturated car-
δ H-1
δ C-1
δ H-4
δ C-4
δ H-1
δ C-1
δ H-2
δ C-2
bohydrate 3 with phenol 4aa
4a
4b
4c
4d
4e
4f
4g
4h
4i
5.82
5.78
5.74
5.82
5.79
5.83
5.76
5.77
5.85
6.01
94.5
94.7
94.6
93.3
93.6
93.4
94.3
93.4
93.2
93.4
4.99
4.94
4.89
4.92
4.91
4.96
4.90
4.88
4.98
5.17
68.1
68.4
68.2
67.3
67.6
67.7
68.4
67,7
67.3
67.3
5.37
5.35
5.28
5.41
5.38
5.43
5.29
5.32
5.43
5.66
99.3
99.6
99.6
98.0
98.6
98.3
99.6
98.7
98.3
98.5
4.91
4.90
4.85
4.82
4.83
4.85
4.78
4.81
4.90
5.10
72.9
73.2
73.5
71.5
72.1
71.5
73.2
72.3
71.7
71.8
Entry
Ligand
Solvent
Time
[h]
Temp
[°C]
Yield
Yield
Yield
5 + 6 [%]
5 [%]b
6 [%]b
1
2
3
4
5
6
dppb
dppb
dppe
PPh3
dppb
dppb
THF
THF
THF
THF
CH3CN
CH2Cl
72
24
24
24
24
24
25
60
60
60
60
35
20
56
74
24
44
46
1
22
6
24
6
21
78
80
48
50
70
24
4j
a
[3]:[4a]:[Pd2(dba)3]:[ligand] = 20:60:1:2.2 (4.4).
Yield refers to isolated pure products after column chromatography.
b
a
Recorded in CDCl3 with TMS as an internal standard.
Scheme 2. Synthesis of 2,3- and 3,4-unsaturated O-glycosides.

36
A. Kubiak et al./Carbohydrate Research 417 (2015) 34–40
Table 3
stereospecific, in all cases, only the β-anomer is formed. The
extension of this very mild methodology of glycosylation to the
synthesis of various di- and trisaccharides is currently under
investigation.
Pd0-catalysed O-arylation reaction unsaturated carbohydrate 3 with phenols 4a–j
according to Scheme 1a
Entry
Phenol
Yield 5 [%]b
Yield 6 [%]b
Yield 5 + 6 [%]
1
2
3
4
5
6
7
8
9
4a
4b
4c
4d
4e
4f
4g
4h
4i
56
47
49
51
15
25
25
22
31
29
22
16
11
22
40
18
41
6
78
63
60
73
55
43
66
28
68
54
1. Experimental
1.1. General methods
All solvents and reagents were purchased from Sigma-Aldrich
and were used as supplied, without additional purification. NMR
spectra were recorded in CDCl3 on Brucer Avance III (600 MHz for
1H NMR, 150 MHz for 13C NMR), coupling constants are reported in
hertz. Chromatographic purification of compounds was achieved
with 230–400 mesh size silica gel. The progress of reactions was
monitored by silica gel thin layer chromatography plates (Merck TLC
Silicagel 60 F254). Optical rotations were measured on a Perkin-
Elmer 241 polarimeter. THF was distilled from sodium/benzophenone
and kept under an argon atmosphere. Reactions involving palladi-
um complexes were carried out in a Schlenk tube under an argon
atmosphere.
37
25
10
4j
a
[3]:[4]:[Pd2(dba)3]:[ligand] = 20:60:1:2.2, THF, 24 h, 60 °C.
Yield refers to isolated pure products after column chromatography.
b
2,3-unsaturated derivative 5d (51%), the isomer 6d was obtained
in 22% yield (Table 3, entry 4).
Coupling of the 4-methylphenol (4e) and the unsaturated
dicarbonate 3 gave O-glycosides in inverse proportion: 5e-15%
and 6e-40% yield (Table 3, entry 5). When 3-metoxyphenol (4f)
was used as the nucleophile, the corresponding products were
obtained with low yield: 5f-25% and 6f-18% (Table 3, entry 6). The
reaction with 4-metoxyphenol (4g), similarly to 4e, afforded pre-
dominantly 3,4-unsaturated isomer 6g (41% yield), while the
2,3-unsaturated isomer 5g was isolated only in 25% yield (Table 3,
entry 7).
The lowest reactivity showed 4-chlorophenol (4h) (Table 3, entry
8). The reaction with this nucleophile gave the O-glycosides 28% total
yield (5h-22%, 6h-6%).
Phenol 4i and 2-naphthol 4j gave products of O-glycosylation
in roughly equivalent proportions (Table 3, entries 9–10).
A plausible reaction pathway for the reaction of dicarbonate 3
with phenols 4a–j is shown in Scheme 3.
2. General procedure for the synthesis of unsaturated
dicarbonate 3
A solution of monosilyl-protected derivative 2a (2 g, 5.2 mmol)
in CH2Cl2 (50 mL) cooled to 0 °C was treated with pyridine (0.53 mL,
6.5 mmol) and isobutyl chloroformate (0.84 mL, 6.5 mmol). After 20 h
at room temperature, the reaction mixture was quenched with water
(30 mL) and extracted with CH2Cl2 (2 × 30 mL). The combined organic
phases were dried (Na2SO4) and evaporated under reduced pres-
sure. The crude product was purified by flash column
chromatography on silica gel to give dicarbonate 3.
The coordination of the Pd(0)-catalyst to the double bond
forms an η2-π-allyl complex. An oxidative addition, during which
the leaving group at the allylic position is expelled, gives an
η3-π-allyl complex. The attack of the nucleophile at the complex
takes place in more reactive anomeric position to form a β-glycosidic
bond, the C-3 position being too crowded. In this way, the
double bond undergoes rearrangement in position 2,3 and it is
possible to create another palladium complex, capable of reacting
with the next molecule of the nucleophile. The attack of the
nucleophile is possible to positions C-2 and C-4 which leads to
2.1. 6-O-tert-Butyldiphenylsilyl-3,4-di-O-isobutyloxycarbonyl-D-
glucal (3)
Colorless oil, 2.62 g, 86% yield, Rf = 0.84 (ethyl acetate/hexane,
7:3), [α]D20 = −5.1 (c 1, CHCl3); 1H NMR (600 MHz, CDCl3): δ = 0.91–0.96
(m, 12H, 2CH(CH3)2), 1.05 (s, 9H, C(CH3)3), 1.93–2.00 (m, 2H,
2CH(CH3)2), 3.85–3.97 (m, 6H, 2H-6, 2OCH2), 4.21 (dd, 1H, J = 11.3,
6.2, H-5), 4.85 (dd, 1H, J = 6.1, 3.4, H-2), 5.26 (dd, 1H, J = 10.3, 5.3,
H-3), 5.393 (t, 1H, J = 6.2, H-4), 6.44 (d, 1H, J = 6.1, H-1), 7.34–7.43
(m, 6H, C6H5), 7.65–7.70 (m, 4H, C6H5); 13C NMR (150 MHz, CDCl3):
δ 18.89 (CH(CH3)2), 18.92 (CH(CH3)2), 19.25 (C(CH3)3), 26.8 (C(CH3)3),
27.9 (CH(CH3)2), 61.5 (C-6), 70.9 (C-3), 71.0 (C-4), 74.3 (OCH2), 74.4
(OCH2), 76.3 (C-5), 97.8 (C-2), 127.8, 127.9, 129.8, 129.9, 133.3, 135.8
(C6H5), 146.5 (C-1), 154.3 (CO), 154.2 (CO). C32H44O8Si (584.77): calcd.
C 65.73, H 7.58; found C 65.69, H 7.51.
the formation of 2,3-unsaturated O-glycoside
unsaturated isomer 6.
5 and 3,4-
In conclusion, we have demonstrated that the 2,3- and
3,4-unsaturated O-glycosides could be obtained in quite good
yields starting from 6-O-tert-butyldiphenylsilyl-3,4-di-O-
isobutyloxycarbonyl-d-glucal (3) and various phenols under neutral
conditions using Pd(0) complex as the catalyst. The reaction is
Scheme 3. Mechanism of Pd(0)-catalysed allylic alkylation reaction.

A. Kubiak et al./Carbohydrate Research 417 (2015) 34–40
37
2.2. General procedure for the Pd0-catalysed alkylation reaction
2.6. 2,3-Dimethylphenyl 6-O-t-butyldiphenylsilyl-2-O-(2,3-
dimethylphenyl)-3,4-dideoxy-β-D-erythro-hex-3-enopyranoside
(6b)
The catalytic system was prepared by stirring Pd2(dba)3 (22.9 mg,
0.025 mmol) and the ligand (0.055 mmol or 0.11 mmol) in an ap-
propriate anhydrous solvent (3 mL) for 0.5 h in a Schlenk tube under
argon. This solution was added, under argon, to a Schlenk tube con-
taining the unsaturated carbohydrate (1 mmol) and phenol (3 mmol)
in solvent (3 mL). The solution was stirred at 25 °C (or 60 °C) and
the reaction was followed by TLC. After an appropriate period of
time, the solvent was evaporated and the residue was
chromatographed on silica gel to give the corresponding O-glycosides.
Colorless oil, 0.05 g, 16% yield, Rf = 0.29 (hexane/dichloromethane,
7:3), [α]D20 = −100 (c 1.0, CHCl3); H NMR (600 MHz, CDCl3): δ 1.05
1
(s, 9H, C(CH3)3), 2.00 (s, 3H, CH3), 2.11 (s, 3H, CH3), 2.22 (s, 3H, CH3),
2.24 (s, 3H, CH3), 3.68 (dd, 1H, J = 10.1, 6.4, H-6a), 3.79 (dd, 1H, J = 10.1,
6.1, H-6b), 4.50–4.54 (m, 1H, H-5), 4.89–4.93 (m, 1H, H-2), 5.36 (d,
1H, J = 5.6, H-1), 5.96 (dt, 1H, J = 10.1, 2.3, H-4), 6.04 (dt, 1H, J = 10.1,
1.5, H-3), 6.77–6,89 (m, 3H, HAr), 6.96–7.05 (m, 3H, HAr), 7.31–7.42
(m, 6H, HAr), 7.62–7.67 (m, 4H, HAr); 13C NMR (150 MHz, CDCl3): δ
19.4 (C(CH3)3), 20.2, 20.3 (CH3), 27.0 (C(CH3)3), 66.3 (C-6), 73.3
(C-2), 75.2 (C-5), 99.6 (C-1), 111.8, 113.2, 123.2, 124.1, 125.9, 126.6,
127.8, 135.8, 138.0, 138.4 (CAr), 125.2 (C-4), 129,9 (C-3), 133.5, 133.7,
155.4, 155.9 (Cq). C38H44O4Si (592.84): calcd. C 76.99, H 7.48; found
C 76.97, H 7.60.
2.3. 2,5-Dimethylphenyl 6-O-t-butyldiphenylsilyl-4-O-(2,5-
dimethylphenyl)-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside
(5a)
Colorless oil, 0.17 g, 56% yield, Rf = 0.70 (hexane/dichloromethane,
1:1), [α]D20 = +9.0 (c 1.0, CHCl3); 1H NMR (600 MHz, CDCl3): δ 1.02
(s, 9H, C(CH3)3), 2.10 (s, 3H, CH3), 2.13 (s, 3H, CH3), 2.23 (s, 3H, CH3),
2.25 (s, 3H, CH3), 3.88 (dd, 1H, J = 10.9, 5.0, H-6a), 3.98 (dd, 1H, J = 10.9,
5.2, H-6b), 4.22 (dd, 1H, J = 10.2, 5.2, H-5), 4.98–4.99 (m, 1H, H-4),
5.82 (s, 1H, H-1), 6.02 (d, 1H, J = 10.2, H-2), 6.20 (ddd, 1H, J = 10.2,
2.4, 1.2, H-3), 6.67–6.80 (m, 3H, HAr), 6.98–7.04 (m, 3H, HAr), 7.21–7.38
(m, 6H, HAr), 7.54–7.66 (m, 4H, HAr); 13C NMR (150 MHz, CDCl3): δ
19.4 (C(CH3)3), 21.5 (CH3), 26.9 (C(CH3)3), 63.6 (C-6), 68.1 (C-4), 76.9
(C-5), 94.5 (C-1), 114.3, 115,8, 122.0, 122.8, 124.8, 135.6, 135.8 (CAr),
127.8 (C-3), 129.8 (C-2), 133.4, 133.5, 155.4, 155.7 (Cq). C38H44O4Si
(592.84): calcd. C 76.99, H 7.48; found C 76.86, H 7.60.
2.7. 2,4-Dimethylphenyl 6-O-t-butyldiphenylsilyl-4-O-(2,4-
dimethylphenyl)-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside (5c)
Colorless oil, 0.14 g, 49% yield, Rf = 0.71 (hexane/ethyl acetate, 9:1);
1H NMR (600 MHz, CDCl3): δ 1.02 (s, 9H, C(CH3)3), 2.10 (s, 3H, CH3),
2.12 (s, 3H, CH3), 2.25 (s, 6H, 2CH3), 3.84 (dd, 1H, J = 10.9, 5.2, H-6a),
3.96 (dd, 1H, J = 10.9, 5.2, H-6b), 4.18 (dd, 1H, J = 10.7, 5.3, H-5),
4.88–4.92 (m, 1H, H-4), 5.74 (s, 1H, H-1), 6.00 (d, 1H, J = 10.7, H-2),
6.14–6.18 (m, 1H, H-3), 6.80–7.16 (m, 6H, HAr), 7.20–7.43 (m, 6H, HAr),
7.52–7.67 (m, 4H, HAr); 13C NMR (150 MHz, CDCl3): δ 19.3 (C(CH3)3),
20.6 (CH3), 26.9 (C(CH3)3), 63.6 (C-6), 68.4 ( C-4), 77.0 (C-5), 94.8 (C-
1), 113.4, 115.2, 127.2, 128.5, 130.5, 131.3, 131.5, 131.9 (CAr), 127.8
(C-3), 129.7 (C-2), 133.4, 153.4, 153.7 (Cq). The compounds 5c and
6c were inseparable. Elemental analysis for a mixture of 5c and 6c
C38H44O4Si (592.84): calcd. C 76.99, H 7.48; found C 77.02, H 7.69.
2.4. 2,5-Dimethylphenyl 6-O-t-butyldiphenylsilyl-2-O-(2,5-
dimethylphenyl)-3,4-dideoxy-β-D-erythro-hex-3-enopyranoside
(6a)
2.8. 2,4-Dimethylphenyl 6-O-t-butyldiphenylsilyl-2-O-(2,4-
Colorless oil, 0.07 g, 22% yield, Rf = 0.74 (hexane/dichloromethane,
1:1), [α]D20 = −126 (c 1.0, CHCl3); 1H NMR (600 MHz, CDCl3): δ 1.05
(s, 9H, C(CH3)3), 2.13 (s, 3H, CH3), 2.16 (s, 3H, CH3), 2.26 (s, 3H,
CH3), 2.29 (s, 3H, CH3), 3.69 (dd, 1H, J = 10.2, 6.2, H-6a), 3.80 (dd,
1H, J = 10.2, 6.2, H-6b), 4.55–4.57 (m, 1H, H-5), 4.90–4.92 (m, 1H,
H-2), 5.37 (d, 1H, J = 5.6, H-1), 5.96 (dt, 1H, J = 10.3, 2.3, H-4), 6.04
(d, 1H, J = 10.3, H-3), 6.69–6,82 (m, 6H, HAr), 6.96–6.99 (m, 6H,
HAr), 7.00–7.34 (m, 4H, HAr) 13C NMR (150 MHz, CDCl3): δ 19.4
(C(CH3)3), 21.5 (CH3), 27.0 (C(CH3)3), 66.4 (C-6), 72.9 (C-2), 75.3
(C-5), 99.3 (C-1), 114.8, 115.8, 122.9, 124.8, 135.8 (CAr), 125.4
(C-4), 129,8 (C-3), 133.5, 133.6 (Cq). C38H44O4Si (592.84): calcd. C
76.99, H 7.48; found C 77.04, H 7.71.
dimethylphenyl)-3,4-dideoxy-β-D-erythro-hex-3-enopyranoside (6c)
Colorless oil, 0.03 g, 11% yield, Rf = 0.71 (hexane/ethyl acetate,
9:1); 1H NMR (600 MHz, CDCl3): δ 1.04 (s, 9H, C(CH3)3), 2.04 (s, 3H,
CH3), 2.14 (s, 3H, CH3), 2.23 (s, 6H, 2CH3), 3.66 (dd, 1H, J = 10.1, 6.4,
H-6a), 3.78 (dd, 1H, J = 10.1, 6.1, H-6b), 4.48–4.51 (m, 1H, H-5),
4.84–4.87 (m, 1H, H-2), 5.29 (d, 1H, J = 5.6, H-1), 5.95 (dt, 1H, J = 10.3,
2.3, H-4), 6.03–6.04 (m, 1H, H-3), 6.80–7.16 (m, 6H, HAr), 7.20–7.43
(m, 6H, HAr), 7.52–7.67 (m, 4H, HAr); 13C NMR (150 MHz, CDCl3): δ
19.3 (C(CH3)3), 20.7 (CH3), 27.1 (C(CH3)3), 66.3 (C-6), 73.3 (C-2), 75.2
(C-5), 99.7 (C-1), 114.8, 115.8, 127.5, 130.6, 131.6 (CAr), 125.3
(C-4), 129,8 (C-3), 133.8, 153.5, 154.1 (Cq).
The compounds 5c and 6c were inseparable. Elemental analy-
sis for a mixture of 5c and 6c C38H44O4Si (592.84): calcd. C 76.99,
H 7.48; found C 77.02, H 7.69.
2.5. 2,3-Dimethylphenyl 6-O-t-butyldiphenylsilyl-4-O-(2,3-
dimethylphenyl)-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside
(5b)
2.9. 3,5-Dimethylphenyl 6-O-t-butyldiphenylsilyl-4-O-(3,5-
dimethylphenyl)-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside
(5d)
Colorless oil, 0.14 g, 47% yield, Rf = 0.20 (hexane/dichloromethane,
7:3), [α]D20 = +170 (c 1.0, CHCl3); 1H NMR (600 MHz, CDCl3): δ 1.02
(s, 9H, C(CH3)3), 2.06 (s, 3H, CH3), 2.09 (s, 3H, CH3), 2.25 (s, 3H, CH3),
2.26 (s, 3H, CH3), 3.85 (dd, 1H, J = 10.9, 5.2, H-6a), 3.98 (dd, 1H,
J = 10.9, 4.8, H-6b), 4.22 (dd, 1H, J = 10.7, 5.2, H-5), 4.94 (ddd, 1H,
J = 6.9, 3.5, 1.5, H-4), 5.78 (d, 1H, J = 1.5, H-1), 6.03 (dt, 1H, J = 10.2,
1.5, H-2), 6.18 (ddd, 1H, J = 10.2, 3.2, 1.5, H-3), 6.77–6.87 (m, 3H, HAr),
6.96–7.01 (m, 2H, HAr), 7.10–7.14 (m, 1H, HAr), 7.21–7.40 (m, 6H, HAr),
7.54–7.66 (m, 4H, HAr); 13C NMR (150 MHz, CDCl3): δ 19.4 (C(CH3)3),
20.2, 20.3 (CH3), 26.9 (C(CH3)3), 63.6 (C-6), 68.4 (C-4), 76.9 (C-5), 94.7
(C-1), 111.2, 112.9, 123.1, 123.8, 126.2, 127.7, 128.5, 135.6, 135.8 (CAr),
127.8 (C-3), 129.8 (C-2), 133.4, 138.4, 155.3, 155.6 (Cq). C38H44O4Si
(592.84): calcd. C 76.99, H 7.48; found C 76.86, H 7.62.
Colorless oil, 0.15 g, 51% yield, Rf = 0.33 (hexane/dichloromethane,
2:1), [α]D20 = −38 (c 1.8, CHCl3); 1H NMR (200 MHz, CDCl3): δ 1.04
(s, 9H, C(CH3)3), 2.23 (s, 6H, 2CH3), 3.85 (dd, 1H, J = 10.8, 5.1, H-6a),
3.98 (dd, 1H, J = 10.8, 5.8, H-6b), 4.21 (dd, 1H, J = 10.2, 5.1, H-5),
4.90–4.95 (m, 1H, H-4), 5.82 (s, 1H, H-1), 5.98 (dd, 1H, J = 10.2, 2.3
H-2), 6.15 (d, 1H, J = 10.2, H-3), 6.61 (m, 6H, HAr), 7.20–7.44 (m, 6H,
HAr), 7.50–7.70 (m, 4H, HAr); 13C NMR (50 MHz, CDCl3): δ 19.3
(C(CH3)3), 21.4 (CH3), 26.9 (C(CH3)3), 63.5 (C-6), 67.3 (C-4), 76.3 (C-5),
93.3 (C-1), 113.6, 114.3, 123.2, 123.9, 127.7, 129.6, 135.5, 135.6 (CAr),
127.6 (C-3), 129.6 (C-2), 133.1, 133.3, 139.1, 139.4, 156.7, 157.5 (Cq).
C38H44O4Si (592.84): calcd. C 76.99, H 7.48; found C 76.88, H 7.71.

38
A. Kubiak et al./Carbohydrate Research 417 (2015) 34–40
2.10. 3,5-Dimethylphenyl 6-O-t-butyldiphenylsilyl-2-O-(3,5-
dimethylphenyl)-3,4-dideoxy-β-D-erythro-hex-3-enopyranoside
(6d)
2.14. 3-Methoxyphenyl 6-O-t-butyldiphenylsilyl-2-O-(3-
methoxyphenyl)-3,4-dideoxy-β-D-erythro-hex-3-enopyranoside (6f)
Colorless oil, 0.12 g, 41% yield, Rf = 0.74 (petroleum ether/
dichloromethane, 1:1), [α]D20 = −72 (c 0.5, CHCl3); 1H NMR (200 MHz,
CDCl3): δ 1.02 (s, 9H, C(CH3)3), 3.72–3.86 (m, 8H, 2OCH3, 2H-6),
4.50–4.54 (m, 1H, H-5), 4.85 (d, 1H, J = 1.9, H-2), 5.29 (s, 1H, H-1),
5.98 ( dt, 1H, J = 10.4, 2.6, H-4), 6.10 (d, 1H, J = 10.4, H-3), 6.52–6.63
(m, 6H, HAr), 7.09–7.10 (m, 2H, HAr), 7.29–7.42 (m, 6H, HAr), 7.57–7.62
(m, 4H, HAr); 13C NMR (50 MHz, CDCl3): δ 19.2 (C(CH3)3), 26.7
(C(CH3)3), 55.2 (OCH3), 66.1 (C-6), 71.5 (C-2), 74.6 (C-5), 98.3 (C-1),
102.5, 102.7, 108.7, 127.6, 128.4, 129.6, 129.9, 130.3, 135.5 (CAr), 123.8
(C-4), 129,9 (C-3), 133.3, 158.1, 158.8, 160.6, 160.9 (Cq). C36H40O6Si
(596.78): calcd. C 72.45, H 6.76; found C 72.37, H 6.74.
Colorless oil, 0.07 g, 22% yield, Rf = 0.43 (hexane/dichloromethane,
2:1); 1H NMR (200 MHz, CDCl3): δ 1.04 (s, 9H, C(CH3)3), 2.24 (s, 6H,
2CH3), 3.67 (dd, 1H, J = 10.0, 6.7, H-6a), 3.76 (dd, 1H, J = 10.0, 6.3,
H-6b), 4.53–4.56 (m, 1H, H-5), 4.82 (bs, 1H, H-2), 5.41 (d, 1H, J = 4.8,
H-1), 5.98 (dd, 1H, J = 10.5, 2.3, H-4), 6.10 (d, 1H, J = 10.5, H-3), 6.62
(s, 6H, HAr), 7.27–7.47 (m, 6H, HAr), 7.58–7.68 (m, 4H, HAr); 13C NMR
(50 MHz, CDCl3): δ 19.2 (C(CH3)3), 21.5 (CH3), 26.8 (C(CH3)3), 66.2
(C-6), 71.5 (C-2), 74.6 (C-5), 98.0 (C-1), 113.9, 114.4, 124.0, 124.1,
127.6, 130.1, 135.6 (CAr), 123.2 (C-4), 129,6 (C-3), 133.2, 133.3, 139.0,
139.3, 157.0, 157.7 (Cq). C38H44O4Si (592.84): calcd. C 76.99, H 7.48;
found C 76.97, H 7.78.
2.15. 4-Methoxyphenyl 6-O-t-butyldiphenylsilyl-4-O-(4-
methoxyphenyl)-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside (5g)
2.11. 4-Methylphenyl 6-O-t-butyldiphenylsilyl-4-O-(4-
methylphenyl)-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside (5e)
Colorless oil, 0.08 g, 25% yield, Rf = 0.22 (hexane/dichloromethane,
2:1), [α]D20 = +25.7 (c 1.8, CHCl3); 1H NMR (600 MHz, CDCl3): δ 1.08
(s, 9H, C(CH3)3), 3.78 (s, 6H, 2OCH3), 3.88 (dd, 2H, J = 10.4, 5.6, 2H-
6), 4.21 (dd, 1H, J = 10.4, 5.2, H-5), 4.85–4.93 (m, 1H, H-4), 5.76 (s,
1H, H-1), 6.06 (d, 1H, J = 10.3, H-2), 6.21 (dd, 1H, J = 10.3, 3.2, H-3),
6.75–7.06 (m, 8H, HAr), 7.27–7.49 (m, 6H, HAr), 7.59–7.73 (m, 4H, HAr);
13C NMR (150 MHz, CDCl3): δ 19.1 (C(CH3)3), 26.7 (C(CH3)3), 55.6
(OCH3), 63.5 (C-6), 68.4 (C-4), 76.3 (C-5), 94.3 (C-1), 114.5, 114.8,
117.2, 128.0, 128.7, 135.6 (CAr), 127.8 (C-3), 129.7 (C-2), 151.0, 151.6,
154.5, 155.0 (Cq). C36H40O6Si (596.78): calcd. C 72.45, H 6.76; found
C 72.51, H 6.74.
Colorless oil, 0.08 g, 15% yield, Rf = 0.34 (hexane/dichloromethane,
1:1), [α]D20 = +91.9 (c 0.6, CHCl3); 1H NMR (200 MHz, CDCl3): δ 1.04
(s, 9H, C(CH3)3), 2.28 (s, 6H, 2CH3), 3.83 (dd, 1H, J = 10.4, 4.7, H-6a),
3.97 (dd, 1H, J = 10.4, 5.6, H-6b), 4.21 (dd, 1H, J = 10.4, 5.2, H-5),
4.91 (dd, 1H, J = 3.7, 3.7, H-4), 5.79 (s, 1H, H-1), 6.02 (d, 1H,
J = 10.3, H-2), 6.17 (dd, 1H, J = 10.3, 3.3, H-3), 6.84–7.09 (m, 8H,
HAr), 7.22–7.45 (m, 6H, HAr), 7.49–7.68 (m, 4H, HAr); 13C NMR
(50 MHz, CDCl3): δ 19.1 (C(CH3)3), 20.4 (CH3), 26.7 (C(CH3)3),
63.6 (C-6), 67.6 (C-4), 76.3 (C-5), 93.6 (C-1), 114.3, 115,8, 116.7,
128.7, 130.1, 135.6, 135.7 (CAr), 127.7 (C-3), 129.9 (C-2), 154.8,
155.4 (Cq). C36H40O4Si (564.79): calcd. C 76.56, H 7.14; found C
76.16, H 7.09.
2.16. 4-Methoxyphenyl 6-O-t-butyldiphenylsilyl-2-O-(4-
methoxyphenyl)-3,4-dideoxy-β-D-erythro-hex-3-enopyranoside (6g)
Colorless oil, 0.05 g, 18% yield, Rf = 0.36 (hexsane/dichloromethane,
2:1), [α]D20 = +92.5 (c 0.6, CHCl3); 1H NMR (200 MHz, CDCl3): δ 1.07
(s, 9H, C(CH3)3), 3.72–3.86 (m, 8H, 2OCH3, 2H-6), 4.44–4.56 (m, 1H,
H-5), 4.72–4.80 (m, 1H, H-2), 5.29 (d, 1H, J = 4.7, H-1), 5.98 (dt, 1H,
J = 10.3, 2.1, H-4), 6.09 (dd, 1H, J = 10.3, 1.3, H-3), 6.74–7.02 (m, 8H,
HAr), 7.24–7.45 (m, 6H, HAr), 7.60–7.70 (m, 4H, HAr); 13C NMR (50 MHz,
CDCl3): δ 19.2 (C(CH3)3), 26.7 (C(CH3)3), 55.6 (OCH3), 66.1 (C-6), 73.2
(C-2), 74.8 (C-5), 99.6 (C-1), 114.5, 114.7, 117.8, 118.2, 128.4, 129.0,
130.0, 135.7 (CAr), 124.6 (C-4), 129,7 (C-3), 151.2, 152.0, 154.6, 155.1
(Cq). C36H40O6Si (596.78): calcd. C 72.45, H 6.76; found C 72.12, H
6.80.
2.12. 4-Methylphenyl 6-O-t-butyldiphenylsilyl-2-O-(4-
methylphenyl)-3,4-dideoxy-β-D-erythro-hex-3-enopyranoside (6e)
Colorless oil, 0.13 g, 40% yield, Rf = 0.40 (hexane/dichloromethane,
1:1), [α]D20 = +24.2 (c 2.0, CHCl3); 1H NMR (200 MHz, CDCl3): δ
1.05 (s, 9H, C(CH3)3), 2.26 (s, 3H, CH3), 2.27 (s, 3H, CH3), 3.67 (dd,
1H, J = 10.1, 6.7, H-6a), 3.76 (dd, 1H, J = 10.1, 6.3, H-6b), 4.50 (ddd,
1H, J = 6.3, 4.5, 2.1, H-5), 4.83 (d, 1H, J = 2.1, H-2), 5.38 (d, 1H,
J = 4.9, H-1), 5.97 (dt, 1H, J = 10.2, 2.8, H-4), 6.08 (d, 1H, J = 10.2,
H-3), 6.84–7.11 (m, 8H, HAr), 7.27–7.45 (m, 6H, HAr), 7.59–7.68 (m,
4H, HAr); 13C NMR (50 MHz, CDCl3): δ 19.1 (C(CH3)3), 20.4 (CH3),
26.7 (C(CH3)3), 66.1 (C-6), 72.1 (C-2), 74.6 (C-5), 98.6 (C-1), 116.2,
116.8, 127.7, 129.9, 130.0, 130.2, 135.7 (CAr), 124.3 (C-4), 129,7
(C-3), 155.0, 155.7 (Cq). C36H40O4Si (564.79): calcd. C 76.56, H 7.14;
found C 76.23, H 7.10.
2.17. 4-Chlorophenyl 6-O-t-butyldiphenylsilyl-4-O-(4-
chlorophenyl)-2,3-dideoxy-β-D-eryhtro-hex-2-enopyranoside (5h)
Colorless oil, 0.07 g, 22% yield, Rf = 0.55 (hexane/dichloromethane,
1:1), [α]D20 = −94 (c 1.0, CHCl3); 1H NMR (600 MHz, CDCl3): δ 1.03
(s, 9H, C(CH3)3), 3.77 (dd, 1H, J = 10.8, 4.6, H-6a), 3.93 (dd, 1H, J = 10.8,
6.4, H-6b), 4.19 (dd, 1H, J = 6.1, 4.6, H-5), 4.87–4.90 (m, 1H, H-4),
5.75 (bs, 1H, H-1), 6.02–6.05 (m, 1H, H-2), 6.13–6.17 (m, 1H, H-3),
6.88–6.94 (m, 4H, HAr), 7.14–7.26 (m, 5H, HAr), 7.29–7.41 (m, 5H, HAr),
7.38–7.61 (m, 4H, HAr); 13C NMR (150 MHz, CDCl3): δ 19.4 (C(CH3)3),
26.9 (C(CH3)3), 55.4 (OCH3), 63.7 (C-6), 67.7 (C-4), 76.9 (C-5), 93.3
(C-1), 117.3, 118.2, 127.4, 129.5, 129.7, 130.0, 135.6, 135.8 (CAr), 127.9
(C-3), 128.7 (C-2), 155.4, 156.2 (Cq). C35H38Cl2O4Si (620.67); MS-EI
m/z: 644.3 [M + Na]+.
2.13. 3-Methoxyphenyl 6-O-t-butyldiphenylsilyl-4-O-(3-
methoxphenyl)-2,3-dideoxy-β-D-erythro-hex-2-enopyranoside (5f)
Colorless oil, 0.08 g, 25% yield, Rf = 0.58 (petroleum ether/
dichloromethane, 1:1), [α]D20 = +17.2 (c 0.5, CHCl3); 1H NMR (600 MHz,
CDCl3): δ 1.03 (s, 9H, C(CH3)3), 3.73 (s, 3H, OCH3), 3.75 (s, 3H, OCH3)
3.85(dd, 1H, J = 10.8, 4.6, H-6a), 3.96 (dd, 1H, J = 10.8, 5.9, H-6b), 4.22
(dd, 1H, J = 10.0, 4.9, H-5), 4.96 (s, 1H, H-4), 5.83 (s, 1H, H-1), 6.03
(d, 1H, J = 10.2, H-2), 6.19 (dd, 1H, J = 10.2, 2.3, H-3), 6.50–6.67 (m,
6H, HAr), 7.10–7.16 (m, 2H, HAr), 7.23–7.33 (m, 6H, HAr), 7.60–7.66 (m,
4H, HAr); 13C NMR (150 MHz, CDCl3): δ 19.4 (C(CH3)3), 26.9 (C(CH3)3),
55.4 (OCH3), 63.7 (C-6), 67.7 (C-4), 76.9 (C-5), 93.4 (C-1), 107.6, 108.9,
125.6, 126.9, 128.4, 129.7, 135.0, 135.6, 158.8, 161.2 (CAr), 127.8 (C-
3), 128.4 (C-2), 133.3, 133.4 (Cq). C36H40O6Si (596.78): calcd. C 72.45,
H 6.76; found C 72.41, H 6.69.
2.18. 4-Chlorophenyl 6-O-t-butyldiphenylsilyl-2-O-(4-
chlorophenyl)-3,4-dideoxy-β-D-erythro-hex-3-enopyranoside (6h)
Colorless oil, 0.02 g, 6% yield, Rf = 0.70 (hexane/dichloromethane,
1:1), [α]D20 = −21.4 (c 0.5, CHCl3); 1H NMR (200 MHz, CDCl3): δ 1.03
(s, 9H, C(CH3)3), 3.65 (dd, 1H, J = 10.3, 6.2, H-6a), 3.73 (dd, 1H,

A. Kubiak et al./Carbohydrate Research 417 (2015) 34–40
39
J = 10.3, 6.2, H-6b), 4.47–4.52 (m, 1H, H-5), 4.80–4.82 (m, 1H,
H-2), 5.32 (d, 1H, J = 5.1, H-1), 5.94 (dt, 1H, J = 10.3, 2.5, H-4), 6.07
(dd, 1H, J = 10.3, 1.4, H-3), 6.86–6.93 (m, 4H, HAr), 7.15–7.26 (m,
5H, HAr), 7.31–7.39 (m, 5H, HAr), 7.58–7.64 (m, 4H, HAr); 13C NMR
(50 MHz, CDCl3): δ 19.4 (C(CH3)3), 26.9 (C(CH3)3), 66.2 (C-6), 72.3
(C-2), 75.1 (C-5), 98.7 (C-1), 117.7, 118.3, 121.1, 118.2, 121.1, 126.8,
127.7, 127.8, 1278.5, 129.5, 130.0 135.6, 135.7 (CAr), 123.9 (C-4),
130.2 (C-3), 133.1, 133.4, 155.6, 156.5 (Cq). C35H38Cl2O4Si (620.67);
MS-EI m/z: 644.3 [M + Na]+.
71.8 (C-2), 75.0 (C-5), 98.5 (C-1), 109.4, 111.3, 119.1, 119.6, 124.1,
126.6, 127.4, 127.8, 129.5, 130.6, 135.7 (CAr), 124.3 (C-4), 129,8 (C-
3), 133.4, 133.5, 154.9 155.7 (Cq); C42H40O4Si (536.73): calcd. C 79.21,
H 6.33; found C 78.98, H 6.42.
Appendix: Supplementary material
Supplementary data to this article can be found online at
doi:10.1016/j.carres.2015.08.016.
2.19. Phenyl 6-O-t-butyldiphenylsilyl-4-O-(phenyl)-2,3-dideoxy-β-
D-erythro-hex-2-enopyranoside (5i)
References
Colorless solid, 0.08 g, 31% yield, Rf = 0.43 (hexane/
dichloromethane, 1:1), m.p. 73.0–73.4 °C, [α]D20 = +7.0 (c 1.0, CHCl3);
1H NMR (200 MHz, CDCl3): δ 1.04 (s, 9H, C(CH3)3), 3.86 (dd, 1H,
J = 10.8, 6.1, H-6a), 3.96 (dd, 1H, J = 10.8, 5.2, H-6b), 4.25 (dd, 1H,
J = 10.8, 5.0, H-5), 4.95–4.99 (m, 1H, H-4), 5.85 (bs, 1H, H-1), 6.06
(d, 1H, J = 10.9, H-2), 6.21 (ddd, 1H, J = 10.9, 3.2, 0.8, H-3), 6.92–
7.08 (m, 6H, HAr), 7.20–7.42 (m, 10H, HAr), 7.54–7.68 (m, 4H, HAr);
13C NMR (50 MHz, CDCl3): δ 19.1 (C(CH3)3), 26.8 (C(CH3)3), 63.6 (C-
6), 67.3 (C-4), 76.4 (C-5), 93.2 (C-1), 115.7, 116.6, 121.4, 122.1, 128.6,
129.3, 135.6 (CAr), 127.6 (C-3), 129.6 (C-2), 133.0, 133.1, 156.7, 157.4
(Cq); C34H36O4Si (536.73): calcd. C 76.08, H 6.76; found C 75.84, H
6.81.
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2.20. Phenyl 6-O-t-butyldiphenylsilyl-2-O-(phenyl)-3,4-dideoxy-β-
D-erythro-hex-3-enopyranoside (6i)
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Colorless oil, 0.10 g, 37% yield, Rf = 0.48 (hexane/dichloromethane
1:1), [α]D20 = −120 (c 1.0, CHCl3); 1H NMR (200 MHz, CDCl3): δ 1.04
(s, 9H, C(CH3)3), 3.67 (dd, 1H, J = 10.1, 6.8, H-6a), 3.78 (dd, 1H, J = 10.1,
6.1, H-6b), 4.49–4.57 (m, 1H, H-5), 4.89–4.91 (m, 1H, H-2), 5.43 (d,
1H, J = 5,0, H-1), 5.98 (dd, 1H, J = 10.5, 2.4, H-4), 6.10 (dd, 1H, J = 10.5,
1.2, H-3), 6.92–7.04 (m, 6H, HAr), 7.17–7.30 (m, 4H, HAr), 7.30–7.46
(m, 6H, HAr), 7.56–7.67 (m, 4H, HAr); 13C NMR (50 MHz, CDCl3): δ 19.2
(C(CH3)3), 26.8 (C(CH3)3), 66.1 (C-6), 71.7 (C-2), 74.7 (C-5), 98.3 (C-
1), 116.1, 121.5, 122.3, 127.6, 129.5, 129.6, 130.2, 135.5 (CAr), 124.1
(C-4), 129,3 (C-3), 133.2, 133.3, 156.9, 157.7 (Cq). C34H36O4Si (536.73):
calcd. C 76.08, H 6.76; found C 75.69, H 6.89.
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2.21. 2-Naphthyl 6-O-t-butyldiphenylsilyl-4-O-(2-naphthyl)-2,3-
dideoxy-β-D-erythro-hex-2-enopyranoside (5j)
Colorless oil, 0.08 g, 29% yield, Rf = 0.60 (dichloromethane/
hexane, 3:2); 1H NMR (600 MHz, CDCl3): δ 1.04 (s, 9H, C(CH3)3), 3.92
(dd, 1H, J = 10.9, 4.8, H-6a), 4.08 (dd, 1H, J = 10.9, 6.3, H-6b), 4.36
(ddd, 1H, J = 6.6, 4.8, 4.2 H-5), 5.17 (dd, 1H, J = 4.1, 4.2, H-4), 6.01
(bs, 1H, H-1), 6.13 (ddd, 1H, J = 10.2, 1.8, 1.3, H-2), 6.30 (ddd, 1H,
J = 10.2, 3.8, 1.4, H-3), 7.23–7.44 (m, 14H, HAr), 7.61–7.77 (m, 10H,
HAr), 13C NMR (150 MHz, CDCl3): δ 19.4 (C(CH3)3), 27.1 (C(CH3)3), 63.9
(C-6), 67.3 ( C-4), 76.5 (C-5), 93.4 (C-1), 109.0, 111.1, 119.2, 123.1,
124.1, 126.6, 127.0, 128.9, 129.8, 135.7, 135.9, 136.2 (CAr), 127.6 (C-
3), 128.9 (C-2), 133.3, 133.4, 155.4, 155.8 (Cq); C42H40O4Si (536.73):
calcd. C 79.21, H 6.33; found C 79.02, H 6.39.
2.22. 2-Naphthyl 6-O-t-butyldiphenylsilyl-2-O-(2-naphthyl)-3,4-
dideoxy-β-D-erythro-hex-3-enopyranoside (6j)
Colorless oil, 0.09 g, 25% yield, Rf = 0.70 (dichloromethane/
hexsane, 3:2), [α]D20 = −45.3 (c 0.5, CHCl3); 1H NMR (600 MHz, CDCl3):
δ 1.02 (s, 9H, C(CH3)3), 3.73 (dd, 1H, J = 10.2, 6.4, H-6a), 3.78 (dd, 1H,
J = 10.2, 6.2, H-6b), 4.61–4.65 (m, 1H, H-5), 5.10 (d, 1H, J = 1.7, H-2),
5.66 (d, 1H, J = 4.8, H-1), 6.11 (dt, 1H, J = 10.4, 2.5, H-4), 6.16 (dt, 1H,
J = 10.4, 1.3, H-3), 7.17–7.44 (m, 14H, HAr), 7.56–7.77 (m, 10H, HAr);
13C NMR (150 MHz, CDCl3): δ 19.4 (C(CH3)3), 27.0 (C(CH3)3), 66.4 (C-6),

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