O- and N-Glycosidation of d-glycals using Ferrier rearrangement under Mitsunobu reaction conditions. Application to N-nucleoside synthesis

Article abstract of DOI:10.1016/j.tet.2011.11.084

We have disclosed the reaction of 3-hydroxy free glycals with O- or N-nucleophiles under Mitsunobu reaction conditions proceeded to produce 2,3-unsaturated glycosides in good to high yield and moderate stereoselectivity. The reaction would take place via

Full text of DOI:10.1016/j.tet.2011.11.084

Tetrahedron 68 (2012) 1092e1096
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O- and N-Glycosidation of -glycals using Ferrier rearrangement under Mitsunobu
D
reaction conditions. Application to N-nucleoside synthesis
*
Kyosuke Michigami, Masahiko Hayashi
Department of Chemistry, Graduate School of Science, Kobe University, Nada, Kobe 657-8501, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
We have disclosed the reaction of 3-hydroxy free glycals with O- or N-nucleophiles under Mitsunobu
reaction conditions proceeded to produce 2,3-unsaturated glycosides in good to high yield and moderate
stereoselectivity. The reaction would take place via allyloxycarbenium ion.
Ó 2011 Elsevier Ltd. All rights reserved.
Received 13 September 2011
Received in revised form 24 November 2011
Accepted 26 November 2011
Available online 3 December 2011
Keywords:
O-Glycosidation
N-Glycosidation
Glycal
Mitsunobu reaction
Ferrier reaction
1. Introduction
of 1,5-anhydro-
of 3-ulose.8 (3) Reduction of 3-keto group. The reaction of 4,6-O-
benzylidene -glucal 1 with p-nitrobenzoic acid in the presence of
DEAD or DMEAD9,10 and PPh3 proceeded to give p-nitrobenzoyl 4,6-
O-benzylidene-2,3-deoxy- -erythro-hex-2-enopyranoside 2 in 70%
D
-erythro-hex-1-en-3-ulose.7 (2) 4,6-Benzylidation
O-Glycosidation and N-glycosidations are fundamental re-
actions in carbohydrate synthesis.1 So far, KoenigseKnorr and its
modified reactions have been used in glycosidation reaction.2,3 On
the other hand, Ferrier reported the glycosidation of 1,2-
unsaturated glycals with nucleophiles in the presence of Lewis
acids leading to the 2,3-unsaturated glycosides.4,5 In Ferrier re-
action the 3-positional group works as a leaving group.
D
D
yield. As for the stereochemistry of the products, the reaction of 1
with p-nitrobenzoic acid in the presence of DEAD and PPh3 at 23 ꢀC
for 1 h in THF gave the product in the ratio of
a
/
b
¼75:25 (78%
yield). The same reaction carried out in toluene at 25 ꢀC gave the
During the course of our study of the synthesis of allose de-
product in
product in
a
/
b
b
¼75:25 (83% yield). The reaction at 0 ꢀC afforded the
rivatives,6 we attempted the inversion of equatorial 3-hydroxy
a
/
¼64:36 (79% yield) as shown in Table 1 (entries 1e3).
group in
D
-glucose derivatives using diethyl azodicarboxylate
4,6-Di-O-acetyl
3,4,6-tri-O-acetyl
the ratio of the product was only moderate compared with the case
of substrate 1. That is, -isomers (4e7) were slightly predominantly
D
-glucal 3 was directly prepared by the reaction of
(DEAD), PPh3, and p-nitrobenzoic acid (Mitsunobu reaction condi-
tions) to obtain the allose derivatives, that is, the 3-hydroxygroup
inversion in the product. However, the product was not a simple
inversion product at 3-position, but O-glycosidation product via the
D
-glucal with lipase at pH 7.0.11 For substrate 3,
a
obtained not only for p-nitrobenzoic acid, but also p-nitrophenol, o-
nitrophenol, and p-isopropylphenol (entries 4e15 in Table 1). It
rearrangement of double bond as a mixture of a- and b-isomers. In
our cases, 3-hydroxy group works as a leaving group. Here, we
report O- and N-glycosidation under Mitsunobu reaction
conditions.
should be noted that the reaction of 4,6-di-O-acetyl D-glucal (3)
with p-nitrobenzoic acid did not proceed neither in the presence of
BF3$OEt2 nor Me3SiOTf. Sobi and Sulikowski reported similar type
of Mitsunobu reaction of glycal with phenolic nucleophiles for
three substrates, that is,
L-rhamnal, D-glucal, and L-fucal de-
2. Results and discussion
rivatives.12 They suggested the reaction proceeded in SN20 manner.
However, we propose SN1 mechanism via allyloxocarbenium ion as
shown Scheme 2. The both of the starting material 1 derived from
4,6-O-Benzylidene
dation of allylic hydroxyl group of
D
-glucal 1 was prepared as follows: (1) oxi-
-glucal leading to the formation
D
D
-glucal and 8 derived from
ratio (
¼75:25) in Scheme 1. This result will indicate the re-
action would proceed via the common intermediate. As for the
D-allal gave the product in same a/
b
a/b
* Corresponding author. Tel.: þ81 78 803 5687; fax: þ81 78 803 5688; e-mail
address: mhayashi@kobe-u.ac.jp (M. Hayashi).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.11.084

K. Michigami, M. Hayashi / Tetrahedron 68 (2012) 1092e1096
1093
Table 1
Glycosidation of protected D
-glucals with oxygen nucleophiles using Mitsunobu reagentsa
Entry
Substrate
NuH
Dialkyl azodicarboxylate (R)
DEAD (Et)
Solvent
THF
Conditions
Temp/ꢀC
Product
Time/h
1
Yieldb (%)
a/
bc
1
1
23
2
78
75:25
2
3
4
5
1
1
3
3
3
3
3
3
3
DEAD
DEAD
DIAD (i-Pr)
DIAD
DMEAD ((CH2)2OCH3)
DMEAD
DMEAD
DMEAD
DMEAD
Toluene
Toluene
THF
Toluene
THF
THF
THF
THF
Toluene
25
0
1
1
1
1
4
18
5
18
3
2
2
4
4
4
4
4
4
4
83
79
82
49
73
67
78
73
74
75:25
66:34
53:47
63:37
61:39
58:42
57:43
58:42
52:48
20
20
20
20
20
20
20
6d
7d
8e
9e
10e
11d
3
DMEAD
DMEAD
THF
THF
20
24
2
5
82
59:41
12d
3
20
6
78
64:36
13e
3
DMEAD
THF
20
24
7
49
58:42
a
All reactions were carried out using 2 equiv of dialkyl azodicarboxylate, PPh3, and nucleophile unless otherwise noted.
b
c
Isolated yield as a mixture of
a and b isomer.
1H NMR analysis.
d
e
Dialkyl azodicarboxylate, PPh3, and nucleophile (1.5 equiv).
Dialkyl azodicarboxylate, PPh3, and nucleophile (1.2 equiv).
Scheme 1. Examination using 4,6-benzylidene-D-allal as a substrate.
difference of stereoselectivity of the product between the case of
substrate 1 ( ¼66:34 to 52:48), we assume
¼75:25) and 3 (
the participation of 4-acetyl group contributed the production of
kinetically favored
-isomer.4e
The formation of triphenylphosphine oxide will be the driving
force to produce allyloxocarbenium ion. This method can be ap-
plied for nitrogen nucleophiles, such as phthalimide, pyrimidinone,
and pyrimidin-thione also worked that led to the novel N-nucleo-
sides (Table 2). In these reactions the products (9e11) were ob-
tained in moderate yield (40e68%) and selectivity (57:43 to 63:37)
(Table 2).
The reaction would proceed via the same intermediate with the
conventional Ferrier reaction, that is, allyloxocarbenium ion. It should
be mentioned that dihydropyrimidinone having non-aromatic
structure did not work as a nucleophile. This may be attributed to
the importance of acidity of nucleophile (NueH) in Scheme 2.
a/b
a/b
b
3. Conclusion
In conclusion, we have revealed O- and N-glycosidation of
D-
glycals under Mitsunobu reaction conditions. Application to the

1094
K. Michigami, M. Hayashi / Tetrahedron 68 (2012) 1092e1096
Scheme 2. Possible mechanism of glycosidation using Mitsunobu reagents.
Table 2
Glycosidation of protected
D
-glucals with nitrogen nucleophiles using Mitsunobu reagentsa
NuH Dialkyl azodicarboxylate
Entry
Substrate
Conditions
Temp/ꢀC
Product
Time/h
Yieldb (%)
a/
bc
1d
3
DMEAD
0
6
9
40
68
57:43
63:37
2
3
3
DMEAD
DMEAD
50
1
10
3
20
24
11
40
60:40
a
All reactions were carried out using 1.2 equiv of dialkyl azodicarboxylate, PPh3, and nucleophile unless otherwise noted.
b
c
Isolated yield as a mixture of
a and b isomer.
1H NMR analysis.
d
Dialkyl azodicarboxylate, PPh3, and nucleophile (1.5 equiv).
novel N-nucleosides synthesis has been also disclosed. Further study
for the synthesis of novel N-nucleosides is now under investigation.
4.2. General procedure
4.2.1. Method A. (using DEAD or DIAD). To a mixture of nucleophile
(0.6 mmol), triphenylphosphine (0.6 mmol) substrate (1 or 3)
(0.5 mmol), and solvent (2.0 mL) was added DEAD (or DIAD)
(0.6 mmol) slowly. After the completion of the reaction, satd
NaHCO3 was added. Extraction with ethyl acetate and the com-
bined organic layers were dried over Na2SO4, and evaporated. The
residue was silica gel column chromatographed to give the product
4. Experimental section
4.1. General
All reactions were carried out in an oven-dried glassware with
magnetic stirring. All starting materials were obtained from com-
mercial sources. 1H and 13C NMR spectra (400 and 100.6 MHz, re-
spectively) were recorded using Me4Si as the internal standard
(0 ppm). Some of the peaks of 13C NMR are overlapped especially in
aromatic regions. The following abbreviations are used: s¼singlet,
d¼doublet, m¼multiplet.
as a mixture of a- and b-isomers.
4.2.2. Method B. (using DMEAD). To a mixture of nucleophile
(0.6 mmol), triphenylphosphine (0.6 mmol), substrate (1 or 3)
(0.5 mmol), and solvent (2.0 mL) was added DMEAD (0.6 mmol)
slowly. After the completion of the reaction, satd NaHCO3 was

K. Michigami, M. Hayashi / Tetrahedron 68 (2012) 1092e1096
1095
added. Organic layers were evaporated and residue was extracted
with diethyl ether and the combined organic layers were dried over
Na2SO4, and evaporated. The residue was silica gel column chro-
170.3; 170.6; 170.7. Anal. Calcd for C19H24O6: C, 65.50; H, 6.94.
Found: C, 65.34; H, 7.01. MS [ESIþ]: m/z: 371.1 [MþNa]þ.
matographed to give the product as a mixture of
a
- and
b
-isomers.
4.2.8. 1-{4,6-Di-O-acetyl-2,3-dideoxy-
enopyranosyl}-phthalimide (9). White solids (40%,
(KBr) 719,1221, 1773 cmꢁ1; 1H NMR (400 MHz, CDCl3);
d
100ꢂ3H, OAc); 2.07 (s, 43/100ꢂ3H, OAc); 2.12 (s, 43/100ꢂ3H, OAc);
2.14 (s, 57/100ꢂ3H, OAc); 4.1e4.2 (m, 37/100H, H5); 4.1e4.3 (m, 2H,
H6; H60); 4.3e4.4 (m, 57/100H, H5); 5.43 (dd, J¼9.2,1.1 Hz, 57/100H,
H4); 5.52 (dd, J¼9.0, 2.2 Hz, 43/100H, H4); 5.8e6.2 (m, 3H, H1; H2;
H3); 7.6e7.8 (m, 2H, ArH); 7.8e8.0 (m, 2H, ArH); 13C NMR (100 MHz,
a
/
b
-
D
-erythro-hex-2-
¼57:43); IR
2.06 (s, 57/
a/b
4.2.3. p-Nitrobenzoyl 4,6-O-benzylidene-2,3-dideoxy-
hex-2-enopyranoside (2). White solids (73%,
¼75:25); IR (KBr)
695, 716, 1096, 1527, 1533, 1720 cmꢁ1 1H NMR (400 MHz, CDCl3);
3.8e4.1 (m, 2H, H5; H6); 4.3e4.4 (m, 2H, H4; H60); 5.64 (s, 75/
a/
b
-D
-erythro-
a/
b
;
d
100H, PhCH); 5.65 (s, 25/100H, PhCH); 5.8e5.9 (m, 1H, H2); 6.39 (d,
J¼9.6 Hz, 1H, H3); 6.59 (s, 75/100H, H1); 6.76 (s, 25/100H, H1);
7.3e7.6 (m, 5H, PhH); 8.2e8.4 (m, 4H, p-NO2C6H4); 13C NMR
CDCl3)
d 20.7; 20.9; 21.0; 62.6; 63.0; 64.6; 70.4; 72.2; 74.3; 74.8;
(100 MHz, CDCl3)
d
66.2; 69.0; 71.3; 74.3; 74.5; 89.7; 96.0; 102.3;
123.6; 123.7; 125.0; 127.4; 128.7; 129.5; 131.6; 131.7; 134.4; 134.5;
166.6; 167.7; 170.0; 170.3; 170.8. HRMS [ESIþ]: m/z calcd for
C18H17NO7Na: 382.0903 [MþNa]þ. Found: 382.0915 [MþNa]þ.
123.6; 124.3; 126.2; 128.4; 129.3; 131.0; 131.1; 133.0; 135.1; 136.7;
163.6. Anal. Calcd for C20H17NO7: C, 62.66; H, 4.47; N, 3.65. Found: C,
62.45; H, 4.55; N, 3.77. MS [ESIþ]: m/z: 406.1 [MþNa]þ.
4.2.9. 1-{4,6-Di-O-acetyl-2,3-dideoxy-a/b-D-erythro-hex-2-
4.2.4. p-Nitrobenzoyl
hex-2-enopyranoside (4). White solids (73%,
1241, 1738, 2969 cmꢁ1 1H NMR (400 MHz, CDCl3);
100ꢂ3H, OAc); 2.06 (s, 58/100ꢂ3H, OAc); 2.0e2.2 (m, 3H, OAc);
4.2e4.4 (m, 3H, H5; H6; H60); 5.19 (dd, J¼4.8, 2.0 Hz, 42/100H, H4);
5.46 (dd, J¼9.6,1.6 Hz, 58/100H, H4); 5.9e6.1 (m, 58/100H, H2); 6.14
(d,1H, H3); 6.2e6.3 (dd, 42/100H, H2); 6.59 (s, 58/100H, H1); 6.68 (s,
42/100H, H1); 8.2e8.4 (m, 4H, ArH); 13C NMR (100 MHz, CDCl3)
4,6-di-O-acetyl-2,3-dideoxy-
¼58:42); IR (KBr)
1.95 (s, 42/
a
/
b
-
D
-erythro-
enopyranosyl}-5-(ethoxycarbonyl)-4,6-diphenyl-pyrimidin-2(1H)-
a/b
one (10). White solids (68%,
a
/
b
¼63:37); IR (KBr) 1231, 1729 cmꢁ1
;
;
d
1H NMR (400 MHz, CDCl3);
d
0.95 (t, J¼7.2 Hz, 3H, CO2CH2CH3); 1.95
(s, 37/100ꢂ3H, OAc); 2.03 (s, 63/100ꢂ3H, OAc); 2.10 (s, 3H, OAc);
4.0e4.5 (m, 5H, H5; H6; H60; CO2CH2CH3); 5.20 (d, J¼3.6 Hz, 37/
100H, H4); 5.52 (d, J¼9.6 Hz, 63/100H, H4); 6.0e6.2 (m, 2H, H2;
H3); 6.92 (s, 63/100H, H1); 6.96 (s, 37/100H, H1); 7.4e7.5 (m, 6H,
ArH); 7.6e7.8 (m, 4H, ArH); 13C NMR (100 MHz, CDCl3)
d 13.4; 20.7;
d
20.7; 20.9; 62.3; 62.7; 63.1; 64.5; 69.4; 73.0; 88.4; 89.6; 97.0; 123.6;
20.9; 61.9; 62.0; 62.5; 63.3; 64.8; 68.8; 72.9; 89.6; 90.8; 120.7;
122.6; 125.7; 126.0; 128.36; 128.41; 128.44; 128.7; 130.27; 130.34;
130.6; 136.8; 137.1; 162.7; 167.3; 167.4; 167.7; 168.1; 170.2; 170.3;
170.7. HRMS [ESIþ]: m/z calcd for C29H28N2O8Na: 555.1743
[MþNa]þ. Found: 555.1709 [MþNa]þ.
125.2; 126.6; 127.7; 130.9; 131.5; 135.0; 150.7; 163.4; 169.9; 170.3;
170.5; 170.7. Anal. Calcd for C17H17NO9: C, 53.83; H, 4.52; N, 3.69.
Found: C, 53.53; H, 4.52; N, 3.78. MS [ESIþ]: m/z: 402.0 [MþNa]þ.
4.2.5. p-Nitrophenyl 4,6-di-O-acetyl-2,3-dideoxy-
2-enopyranoside (5). White solids (82%,
¼59:41); IR (KBr) 1231,
1342,1592,1743, 2958 cmꢁ1; 1H NMR (400 MHz, CDCl3);
1.83 (s, 41/
a/b-D-erythro-hex-
a/b
4.2.10. 1-{4,6-Di-O-acetyl-2,3-dideoxy-
enopyranosyl}-5-(ethoxycarbonyl)-4,6-diphenyl-pyrimidin-2(1H)-
thione (11). Yellow oil (40%,
¼60:40); IR (KBr) 1213, 1515,
1728 cmꢁ1;1HNMR(400 MHz,CDCl3);
0.9e1.0(m, 3H, CO2CH2CH3);
a/b-D-erythro-hex-2-
d
100ꢂ3H, OAc);1.97(s,59/100ꢂ3H,OAc); 2.0e2.2(m, 3H, OAc);4.1e4.4
(m, 3H, H5; H6; H60); 5.15 (dd, J¼5.0, 2.2 Hz, 41/100H, H4); 5.42 (d,
J¼9.6 Hz, 59/100H, H4); 5.82 (s, 59/100H, H1); 5.90 (s, 41/100H, H1);
6.0e6.3 (m, 2H, H2; H3); 7.1e7.2 (m, 2H, ArH); 8.1e8.3 (m, 2H, ArH);
a/b
d
2.00 (s, 60/100ꢂ3H, OAc); 2.02 (s, 40/100ꢂ3H, OAc); 2.10 (s, 60/
100ꢂ3H, OAc); 2.11 (s, 40/100ꢂ3H, OAc); 4.0e4.4 (m, 5H, H5; H6; H60;
CO2CH2CH3); 5.3e5.4 (m, 60/100H, H4); 5.46 (dd, J¼9.0, 1.8 Hz, 40/
100H, H4); 5.8e6.2 (m, 2H, H2; H3); 6.81 (d, J¼2.0 Hz, 60/100H, H1);
6.99 (d, J¼2.0 Hz, 40/100H, H1); 7.4e7.6 (m, 6H, ArH); 7.6e7.8 (d,
13C NMR (100 MHz, CDCl3)
d 20.9; 62.4; 62.9; 63.1; 64.7; 68.3; 72.9;
91.4; 92.6; 115.6; 116.3; 116.6; 125.7; 125.8; 126.1; 128.2; 131.1; 161.6;
161.8;170.0;170.1. Anal. Calcd for C16H17NO8:C, 54.70;H, 4.88;N,3.99.
Found: C, 54.70; H, 4.88; N, 4.07. MS [ESIþ]: m/z: 374.1 [MþNa]þ.
J¼6.8 Hz, 4H, ArH); 13C NMR (100 MHz, CDCl3)
d 20.7; 20.9; 21.0; 62.6;
63.0; 64.6; 70.4; 72.2; 74.3; 74.80; 123.6; 123.7; 125.0; 127.4; 128.7;
129.5; 131.6; 131.7; 134.4; 134.5; 166.6; 167.7; 170.0; 170.3; 170.8.
Anal. Calcd for C29H28N2O7S: C, 63.49; H, 5.11; N, 5.14. Found: C, 63.78;
H, 5.11; N, 5.43. MS [ESIþ]: m/z: 533.1 [MþH]þ; 555.2 [MþNa]þ.
4.2.6. o-Nitrophenyl 4,6-di-O-acetyl-2,3-dideoxy-
2-enopyranoside (6). Yellow oil (78%,
¼64:36); IR (KBr) 1221,
1525, 1592, 1737 cmꢁ1 1H NMR (400 MHz, CDCl3);
1.89 (s, 36/
a/b-D-erythro-hex-
a/b
;
d
100ꢂ3H, OAc); 1.97 (s, 64/100ꢂ3H, OAc); 2.12 (s, 36/100ꢂ3H, OAc);
2.13 (s, 64/100ꢂ3H, OAc); 4.1e4.3 (m, 3H, H5; H6; H60); 5.17 (s, 36/
100H, H4); 5.40 (d, J¼9.2 Hz, 64/100H, H4); 5.74 (s, 64/100H, H1);
5.86 (s, 36/100H, H1); 6.0e6.1 (m, 1H, H2); 6.22 (d, J¼2.0 Hz, 1H,
H3); 7.1e7.2 (m, 1H, ArH); 7.4e7.6 (m, 2H, ArH); 7.8e7.9 (m, 1H,
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific Research
on Innovative Areas, MEXT, Japan ‘Molecular Activation Directed
toward Straightforward Synthesis’ and No. B23350043 from the
MinistryofEducation, Culture, Sports, ScienceandTechnology, Japan.
ArH); 13C NMR (100 MHz, CDCl3)
d 20.4; 20.7; 20.9; 62.5; 63.0; 64.7;
68.3; 73.1; 92.9; 95.0; 118.2; 120.0; 122.2; 122.9; 125.1; 125.9;
126.0; 128.3; 131.0; 133.7; 133.8; 150.2; 170.1; 170.2; 170.3; 170.6.
Anal. Calcd for C16H17NO8: C, 54.70; H, 4.88; N, 3.99. Found: C,
54.70; H, 4.91; N, 4.08. MS [ESIþ]: m/z: 374.1 [MþNa]þ.
References and notes
1. (a) Stick, R. V.; Williams, S. J. Carbohydrates: Essential Molecules of Life, 2nd ed.;
Elsevier: Oxford, Amsterdam, 2009; (b) Sinnott, M. L. Carbohydrate Chemistry
and Biochemistry; RSC Publishing: Cambridge, 2007; (c) The Organic Chemistry
4.2.7. p-Isopropylphenyl 4,6-di-O-acetyl-2,3-dideoxy-
hex-2-enopyranoside (7). White paste (49%,
¼58:42); IR (KBr)
1228,1744, 2961 cmꢁ1; 1H NMR (400 MHz, CDCl3);
1.1e1.3 (m, 6H,
a/b-D-erythro-
a/b
d
€
of Sugars; Levy, D. E., Fugedi, P., Eds.; Taylor & Francis: New York, NY, 2006; (d)
Osborn, H. M. I. Carbohydrates; Academic Press: Oxford, 2003; (e) Glycoscience;
Driguez, H., Thiem, J., Eds.; Springer: Berlin, Heidelberg, New York, NY, 1999; (f)
Prerarative Carbohydrate Chemistry; Hanessian, S., Ed.; Marcel Dekker: New
York, NY, 1997.
CH(CH3)2); 1.85 (s,42/100ꢂ3H, OAc); (s, 58/100ꢂ3H, OAc); 2.1e2.2
(m, 3H, OAc); 2.8e2.9 (m, 1H, CH(CH3)2); 4.1e4.4 (m, 3H, H5; H6;
H60); 5.16 (s, 42/100H, H4); 5.39 (d, J¼10.0 Hz, 58/100H, H4); 5.66
(s, 58/100H, H1); 5.78 (s, 42/100H, H1); 5.9e6.1 (m,1H, H2); 6.1e6.3
2. Koenig, W.; Knorr, E. Ber. 1901, 34, 957e981.
(m, 1H, H3) 7.0e7.2 (m, 4H, ArH); 13C NMR (100 MHz, CDCl3)
d 20.4;
3. Review: (a) Schmidt, R. R. In Comprehensive Organic Synthesis; Trost, B. M.,
Fleming, I., Eds.; Pergamon: Oxford, U.K., 1991; Vol. 6, p 33; (b) Schmidt, R. R.
Angew. Chem. 1986, 98, 213e236; (c) Paulsen, H. Angew. Chem., Int. Ed. Engl. 1982,
21, 155e173; (d) Igarashi, K. Adv. Carbohydr. Chem. Biochem. 1977, 34, 243e283.
20.6; 21.0; 24.1; 33.3; 33.4; 62.7; 63.4; 63.5; 65.1; 67.7; 72.8; 91.9;
93.2; 116.1; 117.0; 125.3; 127.22; 127.24; 129.7; 143.0; 154.9; 155.1;

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4. (a) Ferrier, R. J. J. Chem. Soc., Perkin Trans. 1 1979, 1455e1458; (b) Ferrier, R. J. J.
Chem. Soc. C 1968, 974e977; (c) Ferrier, R. J.; Overend, W. G.; Ryan, A. E. J. Chem.
Soc. C 1962, 3667e3670; (d) Mukherejee, A.; Jayaraman, N. Carbohydr. Res. 2011,
346, 1569e1575; (e) Watanabe, Y.; Itoh, T.; Sakakibara, T. Carbohydr. Res. 2009,
344, 516e520; (f) Ramesh, N. G.; Balasubramanian, K. K. Tetrahedron 1995, 51,
255e272; (g) Procopio, A.; Dalpozzo, R.; De Nino, A.; Nardi, M.; Oliverio, M.;
Russo, B. Synthesis 2006, 2608e2612.
7. Hayashi, M.; Yamada, K.; Arikita, O. Tetrahedron 1999, 55, 8331e8340.
8. Sakakibara, T.; Tsubasa, T.; Kotaka, C.; Kajihara, Y.; Watanabe, Y.; Fujioka, A.
Carbohydr. Res. 2008, 343, 2740e2743.
9. (a) Hagiya, K.; Muramoto, N.; Misaki, T.; Sugimura, T. Tetrahedron 2009,
65, 6109e6114; (b) Sugimura, T.; Hagiya, K. Chem. Lett. 2007, 36,
566e567.
10. Useful reagent for avoiding difficulty of separation of product with co-product.
11. Holla, W. Angew. Chem., Int. Ed. Engl. 1989, 28, 220e221.
12. Sobti, A.; Sulikowski, G. A. Tetrahedron Lett. 1994, 35, 3661e3664 See also;
Guthrie, R. D.; Irvine, R. W.; Davison, B. E.; Henrick, K.; Trotter, J. J. Chem. Soc.,
Perkin Trans. 2 1981, 468e472.
5. Review: (a) Ferrier, R. J. Top. Curr. Chem. 2001, 215, 153e175; (b) Ferrier, R. J.;
€
Zubkov, O. A. Org. React. 2003, 62, 569e736; (c) Vorbruggen, H.; Ruh-Pohlenz,
C. Org. React. 2000, 55, 1e630.
6. Fujiwara, T.; Hayashi, M. J. Org. Chem. 2008, 73, 9161e9164.