Tris(pentafluorophenyl)borane-promoted stereoselective glycosylation with glycosyl trichloroacetimidates under mild conditions

Article abstract of DOI:10.1021/acs.joc.8b00215

Tris(pentafluorophenyl)borane-promoted stereoselective glycosylation with trichloroacetimidate glycosyl donors is described. The reactions proceed efficiently with a wide range of acceptors, from sugar to nonsugar, under mild conditions in the presence of

Full text of DOI:10.1021/acs.joc.8b00215

Subscriber access provided by - Access paid by the | UCSB Libraries
Tris(pentafluorophenyl)borane Promoted Stereoselective Glycosylation
with Glycosyl Trichloroacetimidates under Mild Condition
Dr Kunj Bihari Mishra, Adesh Kumar Singh, and Jeyakumar Kandasamy
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 14 Mar 2018
Downloaded from http://pubs.acs.org on March 14, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 24
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
Tris(pentafluorophenyl)borane Promoted Stereoselective Glycosylation
with Glycosyl Trichloroacetimidates under Mild Condition
Kunj Bihari Mishra, Adesh Kumar Singh and Jeyakumar Kandasamy*
Department of chemistry, Indian Institute of Technology (BHU), Varanasi,
Uttar Pradeshꢀ221005.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
TOC
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Abstract: Tris(pentafluorophenyl)borane promoted stereoselective glycosylation with
trichloroacetimidate glycosyl donors is described. The reactions proceed efficiently with a
wide range of acceptors, from sugar to nonꢀsugar, under mild conditions in the presence of a
catalytic amount of B(C6F5)3. The perbenzylated glucosyl αꢀimidate provides βꢀselective
glycosides in 70ꢀ92% yields.
Structurally wellꢀdefined glycosides are crucial for understanding various biological
functions of carbohydrates.1 Glycosylation is an important reaction through which
enantiomerically pure oligosaccharides and glycoconjugates are synthesized.2 Indeed,
stereoselective formation of a glycosyl linkage is a challenging task which is controlled by
many factors including the nature of donor and acceptor, activator, solvent, temperature,
etc.2,3 Nevertheless, the interaction of the activator with the glycosyl donor or acceptor plays
a crucial role in stereoselective glycosylation.3c,4 Recently, Schmidt et.al have introduced a
novel conceptual approach for the stereoselective glycoside bond formation by acidꢀbase
catalysis, where some promoter shows high affinity towards the acceptor rather than donor
while the adduct of acceptorꢀpromoter activates the glycosyl donor and deliver the acceptor
in a stereocontrolled manner.5
Among the different glycosyl donors, Schmidt’s trichloroacetimidates are most used in
glycosylation due to their high reactivity and easy preparation.2ꢀ6 Activation of
trichloroacetimidate is typically accomplished by Lewis acids such as TMSOTf and boron
trifluoride etherate.4,6 However, these catalysts do not provide stereoselectivity in
glycosylation reactions in the absence of anchimeric assistance. Recently, significant efforts
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 24
1
2
3
4
5
6
7
8
have been made towards the development of transition metal catalysts as well as
organocatalysts to achieve high stereoselectivity in glycosylation reactions.7 Notably, cationic
palladium complexes,8 (salen) cobalt complex,9 gold chlorides,5b silicon fluorides,5c phenyl
boron fluorides,5d thioureas,5e,10 and TMSNTf211 have been recently established.
Nevertheless, each method of glycosylation has its own advantages and disadvantages and
thus the development of new promoters for the glycosylation reaction that offer high
stereoselectivity and good yield under optimum condition is of great interest.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Trisꢀ(pentafluorophenyl)borane (B(C6F5)3 or BCF) is a versatile Lewis acid catalyst explored
in hydrogenation, hydrosilylation, borylation, polymerization reactions, etc.12 Indeed,
B(C6F5)3 is a key reagent leading to the concept of frustrated Lewis pairs.13 Although some
applications of B(C6F5)3 were explored in carbohydrate synthesis,14 its application in
glycosylation reactions are not well studied.15 Recently, the Schmidt group has investigated
the activation of glycosyl imidates by using phenyl boron difluoride which provides good to
excellent stereoselectivity in the glycosylation reaction.5d Nevertheless, these catalysts are
expected to be strong Lewis acids owing to direct boronꢀfluoride (BꢀF) bonds which may be
o
the reason for requirement of low temperature for the activation of imidates (i.e. ꢀ78 C). In
this context, B(C6F5)3 would possess relatively less Lewis acidity and thus we have
envisioned that the imidates may be activated at a more optimal temperature. Moreover,
steric bulk and the electronꢀwithdrawing nature of the three C6F5 groups around the boron
also inspired us to investigate the activation of trichloroacetimidate glycosyl donors with
BCF.
At the outset, glycosylation of perbenzylated glucose αꢀimidate (1a) was investigated with
isoꢀpropanol (2a) in dichloromethane (Table 1). The reaction was carried out at room
°
temperature (~ 23 C) with 10 mol% of tris(pentafluorophenyl)borane in the presence of
molecular sieves (4Å) (Table 1, entry 1). To our delight, the desired glycoside 3a was
obtained in 59% yield within 45 mins while the anomeric selectivity was observed in
α:β=1:3.5 ratio. To our surprise, the glycosylation also proceeds efficiently in the absence of
molecular sieves and gave 3a in 88% yield within 15 mins (Table 1, entry 2). However, there
was no significant change observed in the stereoselectivity. Encouraged, further optimization
of the glycosylation reaction was carried out by varying the reaction conditions in the absence
of molecular sieves. At 0°C, the desired glycoside 3a was obtained in 86% yield with a
significant increase in the βꢀselectivity i.e. from 1:3.5 to 1:9 (α:β) (Table 1, entry 3). To
further explore the effect of temperature, the glycosylation reaction was additionally tested at
ꢀ10°C, ꢀ20°C, ꢀ30°C and ꢀ78°C. The reaction proceeds smoothly at ꢀ10°C to provide the
glycoside 3a in 89% yield with α:β=1:11.5 ratio (Table 1, entry 4). Unfortunately, the
glycosylation reactions were found to be slow at ꢀ20 °C, ꢀ30 °C and ꢀ78 °C (Table 1, entries
ACS Paragon Plus Environment

Page 3 of 24
The Journal of Organic Chemistry
1
2
3
4
5ꢀ7). For instance, the reaction did not proceed to completion even after 14 hours at ꢀ78 °C
(Table 1, entry 7) while ꢀ20°C and ꢀ30°C also gave the products in reduced yields. However,
there was a slight increment in the βꢀselectivity with decrease in temperature.
5
6
7
8
Table 1. Optimization of the reaction condition.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Entry
Tem
(oC)
23
Time
Yield α:βb
(%)a
1c
2
45 mins
15 mins
30 mins
1.5 h
59
1:3.5
1:3.5
1:9
23
0
88
3
86
4
ꢀ10
ꢀ20
ꢀ30
ꢀ78
ꢀ10
ꢀ10
ꢀ10
ꢀ10
ꢀ10
89
1:11.5
1:13
1:19
βꢀonly
1:11.5
nde
5
5.0 h
72
6
5.0 h
60
7
14.0 h
1.5 h
42
8d
9d
10f
11g
12h
82
1.5 h
<10
<10
17
3.0 h
nde
nde
3.0 h
1.5 h
82
1:3
aIsolated yield. Measured using HNMR. Molecular sieves was added. Reaction was
carried out in reverse mode. nd:Not determined. Reaction was carried out in CH3CN.
gReaction was carried out in THF. hBF3.OEt2 is used instead of BCF
b
1
c
d
e
f
All the above mentioned reactions were carried out in normal mode, where the acceptor and
donor were stirred in dichloromethane prior to activator addition. Some recent reports suggest
that reverse mode addition is efficient for glycosylation reactions.5 Thus, the reaction was
tested in two other conditions, namely, i) addition of acceptor and catalyst followed by donor
(Table 1, entry 8) and ii) addition of donor and catalyst followed by acceptor (Table 1, entry
9). In the first case, almost the same yield and stereoselectivity was observed while the latter
condition gave the desired glycoside in <10% yield. Further, the glycosylation reaction was
executed in other solvents such as acetonitrile and THF at ꢀ10oC. Both solvents gave the
desired glycoside 3a in a low yield (Table 1, entries 10 and 11). Finally, the glycosylation
was performed with catalytic amount of BF3.OEt2 (instead of B(C6F5)3) in order to identify
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 24
1
2
3
4
the credential of BCF in seteroselective glycosylation (Table 1, entry 12). The reaction
provides the glycoside 3a in a comparable yield to that of BCF, however with poor
stereoselectivity, i.e. α:β=1:3.
5
6
7
8
9
Scheme 1. B(C6F5)3ꢀpromoted glycosylation of nonꢀsugar and sugar acceptors with donor
1a.a,b,c
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
aDonor 1a (1 equiv.), ROH (1.5 equiv. [2bꢀl] or 0.67 equiv. [2mꢀt]) and BCF (10 mol%)
b
c
1
were stirred in DCM at ꢀ10oC; Isolated yields. α:β ratio was measured using HNMR.
dReaction was carried out with BF3.OEt2 instead of BCF.
Having established the optimized condition, glycosylation of various nonꢀsugar (2bꢀ2l) as
well as sugar acceptors (2mꢀ2t) with perbenzylated glucose αꢀimidate (1a) was investigated
ACS Paragon Plus Environment

Page 5 of 24
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
(Scheme 1). Glycosylation of tertꢀbutanol with donor 1a gave the desired glycoside 3b in
86% yield with α:β ratio 1:19. Further, different linear alcohols including nꢀbutanol, nonanꢀ1ꢀ
ol, hexadecanꢀ1ꢀol, and octadecanꢀ1ꢀol were subjected to the glycosylation with donor 1a
under the optimized condition (Scheme 1, 2cꢀf). The reactions provide the corresponding
glycosides 3cꢀ3f in >76% yields with up to α:β=1:14.7 ratio. It is also noteworthy that the
long chain linear alcohols also showed a comparable reactivity to that of small alcohols in
glycosylation reactions. However, a decrease in βꢀselectivity was observed with the increased
carbon chain length.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Similar to alkanols, allyl, propargyl and benzyl alcohols also underwent glycosylation
smoothly to provide glycosides 3gꢀ3i with good to excellent βꢀselectivity (up to α:β=1:15). It
is important to note that glycosylation of donor 1a with allyl alcohol catalyzed by BF3.OEt2
provides α:β selectivity only in 1:4 ratio. Remarkably, Lꢀmenthol glycoside 3j was obtained
with complete βꢀselectivity with BCF while BF3.OEt2 provides 1:1 anomeric mixture. Steroid
containing glycosides have received considerable attention in various fields.16 The
glycosylation of cholesterol (2k) with donor 1a gave the glycoconjugates 3k in 75% yield
with α:β=1:9 ratio. However, to our surprise, ethisterone (2l) underwent αꢀselective
glycosylation (i.e. α:β =1.9:1), which might be due to the steric hindrance around the
hydroxyl group (Scheme 1, 3l).
Encouraged, glycosylation between sugar alcohols (2mꢀ2t) and donor 1a was investigated
under the optimized condition. Initially, the glycosylation was tested with galactose (2m),
glucose (2n) and mannose (2o) acceptors possessing primary alcohols. To our delight, the
reaction proceeds smoothly and gave the disaccharides 3mꢀ3o in >82% yield while α:β
selectivity was observed up to 1:8.5 ratio. Similarly, glycosylation of secondary alcohol
possessing mannopyranose (2p) and glucopyranose acceptors (2q and 2r) was successfully
accomplished in >78% yield with α:β=1:2 to 1:9 ratio (Scheme 1, 3pꢀ3r). The reaction also
proceeds with diol containing acceptor such as 2,6ꢀbenzylidene αꢀmethylglucoside (2s) and
gave βꢀselective disaccharides 3sa (3ꢀOH glycosylated) and 3sb (2ꢀOH glycosylated) in 51%
and 29% yield, respectively. However, isoꢀpropylidene protected Dꢀglucose acceptor (2t)
gave the αꢀselective glycoside (3t) (α:β =5.5:1). In fact, a similar observation was previous
reported by Schmidt et.al where acceptor 2t provides preferentially αꢀselective glycoside
with perbenzyl glucosyl αꢀimidate due to steric hindrance and poor reactivity of hydroxyl
group (i.e. 3ꢀOH).6c
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 24
1
2
3
Scheme 2. B(C6F5)3ꢀpromoted glycosylation of various glycosyl imidates with different
acceptors.a
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
aDonor 1a (1 equiv.), ROH (1.5 equiv.,) for 2n (0.67 equiv.) and BCF (10 mol%) were stirred
in DCM ꢀ10oC. bIsolated yield. cMeasured using 1HNMR.
Having studied the acceptor scope with perbenzylated glucose αꢀimidate, the scope of donors
was investigated with other commonly used glycosyl imidates 1bꢀ1g (Scheme 2). Initially,
glycosylation of different acceptors with perbenzylated glucose βꢀimidate (1b) was studied.
Glycosylation of isoꢀpropanol with donor 1b gave the glycoside 3a in 90% yield, however
with high αꢀselectivity (α:β=3:1). Similarly, acceptors Lꢀmenthol (2j) and αꢀmethylglucoside
2n were also gave the glycosides 3j and 3n with increased αꢀselectivity in comparison to the
reactions of these acceptors with glucose αꢀimidate (1a). Further, the glycosylation of isoꢀ
propanol (2a) was investigated with perbenzylated glalactosyl and mannosyl α/βꢀimidates to
understand the anomeric selectivity (Scheme, 1cꢀ1e). Similar to our previous observation,
galactose αꢀimidate (1c) underwent glycosylation with high βꢀselectivity (Scheme 3, 3u). On
the other hand, perbenzylated mannose αꢀ and βꢀimidates (1d and 1e) gave high βꢀ and αꢀ
selective glycosides 3v and 3w, respectively. Further, the glycosylation was investigated with
ACS Paragon Plus Environment

Page 7 of 24
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
participating group containing donor such as 2ꢀOꢀbenzoylꢀ3,4,6ꢀtriꢀOꢀbenzylglucose αꢀ
imidate (1f) and 2ꢀOꢀbenzoylꢀ3,4,6ꢀtriꢀOꢀbenzylmannose βꢀimidate (1g) donors in the
presence of nꢀbutanol (2c) and cyclohexanol (2s) acceptors. All the reactions proceeded
smoothly to provide the desired products 4aꢀ4d in >87% yield with complete stereocontrol
(either α or β).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The mechanism of the reaction is unclear to us at this point of time. However, from scheme 1
and 2, it is clear that the αꢀimidates provide high βꢀselectivity while increased αꢀselectivity is
2
observed with βꢀimidates. Therefore, we believe that the reaction might proceed through SN
or acidꢀbase mechanism rather than SN1 (i.e. through carbonium ion intermediate). In this
1
context, H NMR study was performed with the acceptor (isoꢀpropanol) in the presence of
and absence of promoter B(C6F5)3 (1.0 equiv.) at room temperature in CDCl3. It reveals that
there is a formation of acceptorꢀactivator adduct which can be seen from the shift of the OH
peak of isoꢀpropanol in the presence of B(C6F5)3 (Figure SIꢀ1 in ESI). In addition, under
moisture free condition, the donor 1a did not undergo decomposition at ꢀ10oC in the presence
of 10 mol% of B(C6F5)3. In fact, similar observations were previously reported with other
acidꢀbase catalysts such as phenylboron difluoride as well as gold chloride.5b,5d Therefore,
overall it lends support to the assumption that the BCF may act as an acidꢀbase type rather
than simple SN2 type reaction. At first, acceptor forms adduct with catalyst which activates
the imidate in a stereoselective manner to provide βꢀselective glyscosides from perbenzylated
αꢀglucosyl imidate as shown in scheme 3.
Scheme 3. Plausible mechanism for the activation of imidates with BCF.
In conclusion, we have demonstrated the application of tris(pentafluorophenyl)borane as an
efficient catalyst for stereoselective glycosylation with glycosyl imidates. A wide range of
sugar and nonꢀsugar acceptors were examined with perbenzylated αꢀglucosyl imidate as well
as different αꢀ and βꢀglycosyl imidates. All the reactions proceed in a stereoselective manner
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 24
1
2
3
4
where αꢀimidates give βꢀselective glycosides while βꢀimidates provide αꢀselective glycosides
in high yields. This simple method does not require molecular sieves or extremely low
temperatures, and thus shows promise to find wide applications in oligosaccharide synthesis.
5
6
7
8
9
Experimental Section
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
General methods
All the reactions were executed using anhydrous solvents under an argon atmosphere in
ovenꢀdried glassware at 100°C. All the reagents and solvents were of pure analytical grade.
Thinꢀlayer chromatography (TLC) was performed on 60 F254 silica gel, preꢀcoated on
aluminum plates and revealed with either a UV lamp (λmax = 254 nm) or a specific colour
reagent (iodine vapours) or by spraying with methanolic H2SO4 solution and subsequent
charring by heating at 100°C. H and 13C NMR were recorded at 500 MHz and 125 MHz,
1
respectively on Bruker Advance 500 MHz NMR spectrometer. Chemical shifts given in ppm
downfield from internal TMS; J values in Hz. HRMS spectra was recorded on UHD QꢀTOF
using water’s Quattro Micro V 4.1. Column chromatography was performed using 100ꢀ200
mess silica gel.
Experimental Procedures
Optimization Table 1, Entry 1: Anhydrous DCM (6 mL) was added to a powdered, flameꢀ
dried 4 Å molecular sieves (250 mg), followed by the addition of donor 1a (120 mg, 0.18
mmol) and isoꢀpropanol (acceptor) 2a (0.016 ml, 0.27 mmol). The reaction mixture was
stirred for 5 mins at room temperature to which the activator BCF (10 mg, 0.018 mmol) was
added. The reaction was further stirred for 45 minutes at this temperature. After completion,
the reaction was quenched by addition of triethylamine (0.1 ml) and diluted with 50 mL of
DCM. The organic layer was washed with NaHCO3 (aq.), brine and dried over Na2SO4.
Further the organic layer was filtered, concentrated and subjected for the column
chromatography purification (hexane/ethyl acetate) using silica gel (SiO2:100ꢀ200) to afford
the glycoside 3a.
Optimization Table 1, Entries 2ꢀ7: Glucosyl donor 1a (120 mg, 0.18 mmol) and isoꢀ
propanol 2a (0.016 ml, 0.27 mmol) were stirred in freshly dried DCM (4 mL) at room
temperature for 5 mins. After that, the reaction mixture was cooled to appropriate
temperature as stated in Optimization Table 1. The reaction mixture was stirred for 5 mins at
the same temperature to which the activator BCF (10 mg, 0.018 mmol) was added. The
reaction mixture was further stirred for appropriate time as stated in Optimization Table 1 and
quenched by addition of triethylamine (0.1 ml) and diluted with 50 mL of DCM. The organic
layer was washed with NaHCO3 (aq.), brine and dried over Na2SO4. Further the organic layer
ACS Paragon Plus Environment

Page 9 of 24
The Journal of Organic Chemistry
1
2
3
4
was filtered, concentrated and subjected for the column chromatography purification
(hexane/ethyl acetate) using silica gel (SiO2:100ꢀ200) to afford the glycoside 3a in different
yields as stated in optimization Table.
5
6
7
8
9
Optimization Table 1, Entry 8: isoꢀPropanol 2a (0.016 ml, 0.27 mmol) and the activator
BCF were stirred in freshly dried DCM (3 mL) at room temperature for 5 mins. After that the
reaction mixture was cooled to ꢀ10oC. The reaction mixture was stirred for 5 mins at the same
temperature to which the solution glucosyl donor 1a (120 mg, 0.18 mmol) in DCM (1 mL)
was added. The reaction mixture was further stirred for 1.5 h at the same temperature, and
quenched by addition of triethylamine and diluted with 50 mL of DCM. The organic layer
was washed with NaHCO3 (aq.), brine and dried over Na2SO4. Further the organic layer was
filtered, concentrated and subjected for the column chromatography purification
(hexane/ethyl acetate) using silica gel (SiO2:100ꢀ200) to afford the glycoside 3a.
Optimization Table 1, Entry 9: Glucosyl donor 1a (120 mg, 0.18 mmol) and the activator
BCF were stirred in freshly dried DCM (3 mL) at room temperature for 5 mins. After that the
reaction mixture was cooled to ꢀ10oC. The reaction mixture was stirred for 5 mins at the same
temperature to which the solution of isoꢀpropanol 2a (0.016 ml, 0.27 mmol) in DCM (1 mL)
was added. The reaction mixture was further stirred for 1.5 h at the same temperature.
Decomposition of the donor was observed.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Optimization Table 1, Entries 10ꢀ11: A similar procedure was adopted as stated above in
optimization table 1, entry 2ꢀ7. However, in the place of DCM, other solvents such as THF
and acetonitrile were used for the glycosylation reaction.
Optimization Table 1, Entry 12: Anhydrous DCM (6 mL) was added to a powdered, flameꢀ
dried 4 Å molecular sieves (250 mg), followed by the addition of donor 1a (120 mg, 0.18
mmol) and isoꢀpropanol (acceptor) 2a (0.016 ml, 0.27 mmol). The reaction mixture was
stirred for 5 mins at ꢀ10oC to which the activator BF3. OEt2 (cat.) was added. The reaction
was further stirred for 90 minutes at this temperature. After completion, the reaction was
quenched by addition of triethylamine (0.1 ml) and diluted with 50 mL of DCM. The organic
layer was washed with NaHCO3 (aq.), brine and dried over Na2SO4. Further the organic layer
was filtered, concentrated and subjected for the column chromatography purification
(hexane/ethyl acetate) using silica gel (SiO2:100ꢀ200) to afford the glycoside 3a.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 24
1
2
General Glycosylation Procedures:
3
4
5
6
7
8
9
Glycosylation Procedure A (for nonsugar acceptors 2bꢀ2l and 2s, Scheme 1 and 2): Donor (1
equiv.) and acceptor (1.5 equiv) were stirred in freshly dried DCM (3ꢀ5 mL) for 5 mins at
room temperature. After 5 mins, the reaction mixture was cooled to ꢀ10 oC and allowed to stir
for 5 mins, to which the activator BCF (0.1 equv. with respect to donor) was added. The
reaction was further stirred for 1.5 h at the same temperature and quenched by addition of
triethylamine (0.1 mL) and diluted with 50 mL of DCM. The organic layer was washed with
NaHCO3 (aq.) and brine, dried over Na2SO4, filtered, and concentrated. The residue was
purified by column chromatography (hexane/ethyl acetate) using silica gel (SiO2:100ꢀ200) to
afford glycosides.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Glycosylation Procedure B (For sugar acceptors 2mꢀ2t, Scheme 1 and 2): Glycosyl donor (1
equiv) and acceptor (0.67 equiv.) were stirred in freshly dried DCM (3ꢀ5 mL) for 5 mins at
room temperature. After 5 mins, the reaction mixture was cooled to ꢀ10 oC and allowed to stir
for 5 mins, to which the activator BCF (0.1 equiv. with respect to acceptor) was added. The
reaction was further stirred for 1.5 h at the same temperature and quenched by addition of
triethylamine (0.1 mL) and diluted with 50 mL of DCM. The organic layer was washed with
NaHCO3 (aq.) and brine, dried over Na2SO4, filtered, and concentrated. The residue was
purified by column chromatography (hexane/ethyl acetate) using silica gel (SiO2:100ꢀ200) to
afford glycosides.
2ꢀPropyl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranoside [3a]5c: The compound 3a was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1a
(120 mg, 0.18 mmol) and isoꢀpropanol 2a (0.016 ml, 0.27 mmol) in freshly dried DCM (4
o
mL) in the presence of BCF (10 mg, 0.018 mmol) at ꢀ10 C. Column chromatography
purification was performed using 5% ethyl acetate in hexane to obtain 3a as white solid (83
mg, 89%); α:β=1:11.5; TLC Rf = 0.35 (12% ethyl acetate/88% hexane); 1H NMR (500 MHz,
CDCl3) δ 7.25ꢀ7.16 (m, 18H), 7.09 (d, J = 6.3 Hz, 2H), 4.87 (dd, J = 25.5, 10.5 Hz, 2H), 4.72
(dd, J = 18.5, 10.5 Hz, 2H), 4.63 (d, J = 10.5 Hz, 1H), 4.52ꢀ4.44 (m, 3H), 4.39 (d, J = 7.5 Hz,
1H), 3.96ꢀ3.93 (m, 1H), 3.65 (d, J = 10.5 Hz, 1H), 3.59ꢀ3.54 (m, 2H), 3.47 (t, J = 9.5 Hz,
1H), 3.39ꢀ3.37 (m, 2H), 1.24 (d, J = 6.0 Hz, 3H), 1.17 (d, J = 9.5 Hz, 3H); 13C NMR (125
MHz, CDCl3) δ 138.6, 138.5, 138.2, 138.1, 128.3, 128.3, 128.3, 128.1, 127.9, 127.8, 127.7,
127.6, 127.6, 127.5, 127.5, 102.1, 84.8, 82.2, 77.9, 75.6, 74.9, 74.8, 74.7, 73.4, 72.3, 69.1,
23.7, 22.2.
tꢀButyl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranoside [3b]17a: The compound 3b was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1a
(100 mg, 0.15 mmol) and tꢀbutanol 2b (17 mg, 0.23 mmol) in freshly dried DCM (3 mL) in
the presence of BCF (8 mg, 0.015 mmol) at ꢀ10 oC. Column chromatography purification was
ACS Paragon Plus Environment

Page 11 of 24
The Journal of Organic Chemistry
1
2
3
4
performed using 8% ethyl acetate in hexane which furnished 3b as white solid (76 mg, 86%);
1
α:β= 1:19; TLC Rf = 0.45 (15% ethyl acetate/85% hexane); H NMR (500 MHz, CDCl3) δ
7.27ꢀ7.17 (m, 18H), 7.10 (d, J = 6.0 Hz, 2H), 4.90 (d, J = 11.0 Hz, 1H), 4.84 (d, J = 10.5 Hz,
1H), 4.72 (dd, J = 19.5, 11.0 Hz, 2H), 4.63 (d, J = 11.0 Hz, 1H), 4.52ꢀ4.45 (m, 4H), 3.63 (d, J
= 10.5 Hz, 1H), 3.59ꢀ3.53 (m, 2H), 3.45 (t, J = 9.0 Hz, 1H), 3.39ꢀ3.33 (m, 2H), 1.50 (s,
0.76H), 1.25 (s, 8.52H); 13C NMR (125 MHz, CDCl3) δ 138.6, 138.4, 138.3, 138.1, 128.3,
128.2, 128.1, 127.9, 127.8, 127.6, 127.5, 127.4, 97.8, 85.1, 82.3, 78.1, 76.0, 75.7, 74.9, 74.8,
74.6, 73.3, 69.3, 28.8.
Butyl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranoside [3c]17b: The compound 3c was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1a
(112 mg, 0.16 mmol) and nꢀbutanol 2c (0.019 ml, 0.24 mmol) in freshly dried DCM (4 mL)
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
o
in the presence of BCF (8 mg, 0.016 mmol) at ꢀ10 C. Column chromatography purification
was performed using 5% ethyl acetate/hexane which furnished 3c as white solid (83 mg,
88%); α:β=1:14.7; TLC Rf = 0.35 (10% ethyl acetate in hexane); 1H NMR (500 MHz, CDCl3)
δ 7.39ꢀ7.28 (m, 18H), 7.20 (d, J = 7.5 Hz, 2H), 4.98 (t, J = 11.5 Hz, 2H), 4.84 (dd, J = 15.5,
10.5 Hz, 2H), 4.76 (d, J = 11.0 Hz, 1H), 4.64ꢀ4.56 (m, 3H), 4.43 (d, J = 7.5, 1H), 4.02ꢀ4.00
(m, 1H), 3.79 (d, J = 11 Hz, 1H), 3.73ꢀ3.66 (m, 2H), 3.63ꢀ3.58 (m, 2H), 3.50 (dd, J = 15.5,
6.5 Hz, 2H), 1.71ꢀ1.67 (m, 2H), 1.49ꢀ1.46 (m, 2H), 0.98 (t, J = 7.5 Hz, 3H); 13C NMR (125
MHz, CDCl3) δ 138.7, 138.5, 138.2, 138.1, 128.4, 128.3, 128.2, 128.0, 127.9, 127.7, 127.7,
127.6, 127.6, 103.7, 84.7, 82.3, 78.0, 75.7, 75.0, 74.9, 74.8, 73.5, 69.8, 69.0, 31.8, 19.3, 13.9.
Nonyl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranoside, [3d]: The compound 3d was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1a
(120 mg, 0.18 mmol) and acceptor 2d (0.048 ml, 0.27 mmol) in freshly dried DCM (4 mL),
o
in the presence of BCF (9 mg, 0.018 mmol) at ꢀ10 C. Column chromatography purification
was performed using 3% ethyl acetate in hexane which furnished 3d as semi solid (104 mg,
85%); α:β=1:12.2; TLC Rf = 0.35 (8% ethyl acetate in hexane); 1H NMR (500 MHz, CDCl3)
δ 7.43ꢀ7.32 (m, 18H), 7.23 (dd, J = 8.0, 2.0 Hz, 2H), 5.02 (dd, J = 15.0, 11.0 Hz, 2H), 4.87
(dd, J = 14.5, 10.5 Hz, 2H), 4.79 (d, J = 11.0 Hz, 1H), 4.69ꢀ4.59 (m, 3H), 4.46 (d, J = 8.0 Hz,
1H), 4.06ꢀ4.01 (m, 1H), 3.81 (dd, J = 11.0, 2.0 Hz, 1H), 3.75ꢀ3.70 (m, 2H), 3.65 (m, 2H),
3.54ꢀ3.52 (m, 2H), 1.75ꢀ1.68 (m, 2H), 1.49ꢀ1.44 (m, 2H), 1.38ꢀ1.33 (m, 10H), 0.95 (t, J =
13
6.5 Hz, 3H); C NMR (125 MHz, CDCl3) δ 138.5, 138.4, 138.1, 138.0, 128.2, 128.2, 128.2,
128.0, 127.8, 127.7, 127.6, 127.4, 103.6, 84.6, 82.2, 77.8, 75.6, 74.9, 74.8, 74.7, 73.4, 70.0,
68.9, 31.8, 29.7, 29.4, 29.4, 29.2, 26.1, 22.6, 14.0; HRMS (ESIꢀTOF) m/z: [M + H]+ Calcd
for C43H55O6 667.3999, found 667.4001.
Hexadecanyl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranoside, [3e]17c: The compound 3e
was prepared using the glycosylation procedure A. The reaction was carried out between
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 24
1
2
3
4
donor 1a (110 mg, 0.16 mmol) and hexadecanol acceptor 2e (58 mg, 0.24 mmol) in freshly
o
dried DCM (5 mL) in the presence of BCF (8 mg, 0.016 mmol) at ꢀ10 C. Column
chromatography purification was performed using 3% ethyl acetate in hexane which
5
6
7
8
furnished 3e as White Semi solid (97 mg, 80%); α:β=1:9; TLC Rf = 0.4 (8% ethyl
1
acetate/92% hexane); H NMR (500 MHz, CDCl3) δ 7.38ꢀ7.28 (m, 18H), 7.18 (dd, J = 7.5,
9
2.0 Hz, 2H), 4.97 (dd, J = 13.5, 11.0 Hz, 2H), 4.82 (dd, J = 15.5, 10.9 Hz, 2H), 4.74 (d, J =
11.0 Hz, 1H), 4.63ꢀ4.54 (m, 3H), 4.41 (d, J = 7.5 Hz, 1H), 4.01ꢀ3.97 (m, 1H), 3.78 (dd, J =
10.5, 2.0 Hz, 1H), 3.70ꢀ3.65 (m, 2H), 3.60 (m, 2H), 3.49ꢀ3.47 (m, 2H), 1.71ꢀ1.65 (m, 2H),
1.44ꢀ1.38 (m, 2H), 1.32ꢀ1.27 (m, 21H), 0.91 (t, J = 7.0 Hz, 3H); 13C NMR (125 MHz,
CDCl3) δ 138.6, 138.5, 138.2, 138.1, 128.3, 128.3, 128.3, 128.1, 127.9, 127.8, 127.7, 127.5,
103.6, 84.7, 82.2, 77.9, 75.6, 74.9, 74.8, 74.7, 73.4, 70.1, 69.0, 31.9, 29.7, 29.7, 29.6, 29.6,
29.4, 29.3, 26.1, 22.6, 14.1.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Octadecayl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranoside, [3f]: The compound 3f was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1a
(100 mg, 0.15 mmol) and ocatdecanol acceptor 2f (62 mg, 0.23 mmol) in freshly dried DCM
o
(5 mL) in the presence of BCF (8 mg, 0.015 mmol) at ꢀ 10 C. Column chromatography
purification was performed using 3% ethyl acetate in hexane which furnished 3f as semi solid
1
(95 mg, 76%); α:β=1:7; TLC Rf=0.45 (8% ethyl acetate/92% hexane); H NMR (500 MHz,
CDCl3) δ 7.37ꢀ7.29 (m, 20H), 4.97 (dd, J = 13.5, 11.0 Hz, 2H), 4.82 (dd, J = 15.0, 10.5 Hz,
2H), 4.74 (d, J = 10.5 Hz, 1H), 4.65ꢀ4.54 (m, 3H), 4.41 (d, J = 7.5 Hz, 1H), 4.01ꢀ3.96 (m,
1H), 3.76 (dd, J = 10.5, 1.5 Hz, 1H), 3.71ꢀ3.65 (m, 2H), 3.61ꢀ3.58 (m, 2H), 3.49ꢀ3.47 (m,
2H), 1.67 (m, 2H), 1.42ꢀ1.40 (m, 2H), 1.32ꢀ1.28 (m, 27H), 0.90 (t, J = 6.5 Hz, 3H); 13C NMR
(125 MHz, CDCl3) δ 138.6, 138.5, 138.2, 138.1, 128.3, 128.3, 128.3, 128.1, 127.9, 127.8,
127.7, 127.5, 103.6, 84.7, 82.2, 77.9, 75.6, 74.9, 74.8, 74.7, 73.4, 70.1, 69.0, 31.9, 29.7, 29.7,
29.6, 29.6, 29.4, 29.3, 26.2, 22.6, 14.1; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for
C52H72O6Na 815.5227, found 815.5267.
Allyl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranoside, [3g]5c: The compound 3g was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1a
(115 mg, 0.17 mmol) and ocatdecanol acceptor 2g (0.023 ml, 0.34 mmol) in freshly dried
DCM (5 mL) in the presence of BCF (9 mg, 0.017 mmol) at ꢀ 10 oC. Column
chromatography purification was performed using 5% ethyl acetate in hexane which
furnished 3g as semi solid (81 mg, 83%); α:β=1:13.5; TLC Rf=0.45 (8% ethyl acetate/92%
hexane);1H NMR (500 MHz, CDCl3) δ 7.42 – 7.30 (m, 18H), 7.23 – 7.21 (m, 2H), 6.07 –
5.99 (m, 1H), 5.43ꢀ5.39 (m, 1H), 5.28 – 5.25 (m, 1H), 5.02 (dd, J = 17.5, 11.0 Hz, 2H), 4.87
(dd, J = 15.0, 11.0 Hz, 2H), 4.79 (d, J = 11.0 Hz, 1H), 4.68 (d, J = 12.0 Hz, 1H), 4.61 (dd, J =
11.5, 9.0 Hz, 2H), 4.53 – 4.49 (m, 2H), 4.24ꢀ4.19 (m, 1H), 3.82 – 3.65 (m, 4H), 3.58 – 3.51
ACS Paragon Plus Environment

Page 13 of 24
The Journal of Organic Chemistry
1
2
3
4
(m, 2H); 13C NMR (125 MHz, CDCl3) δ 138.5, 138.4, 138.1, 138.0, 134.0, 128.3, 128.3,
128.1, 127.9, 127.8, 127.7, 127.6, 127.6, 127.5, 117.1, 102.6, 84.6, 82.2, 77.8, 75.6, 74.9,
74.8, 73.4, 70.2, 68.9.
5
Propargyl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranoside, [3h]5e: The compound 3h was
prepared using the glycosylation procedure A: The reaction was carried out between donor 1a
(118 mg, 0.17 mmol) and propargyl alcohol acceptor 2h (0.014 ml, 0.25 mmol) in freshly
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
o
dried DCM (4 mL) in the presence of BCF (10 mg, 0.017 mmol) at ꢀ10 C. Column
chromatography purification was performed using 7% ethyl acetate in hexane which
furnished 3h as viscous oil (68 mg, 70%); α:β=1:7.5; TLC Rf = 0.35 (10% ethyl acetate/90%
hexane); 1H NMR (500 MHz, CDCl3) δ 7.45ꢀ7.31 (m, 18H), 7.22ꢀ7.20 (m, 2H), 5.01 (dd, J =
23.5, 11.0 Hz, 2H), 4.85 (dd, J = 19.0, 10.5 Hz, 2H), 4.75 (d, J = 10.5 Hz, 1H), 4.70ꢀ4.65 (m,
2H),4.60 (d, J = 3.5 Hz, 1H), 4.58 (d, J = 2.0 Hz, 2H), 4.51ꢀ4.50 (m, 1H), 4.32 (d, J = 2.0 Hz,
0.18H), 3.78ꢀ3.67 (m, 4H), 3.54ꢀ3.53 (m, 2H), 2.51 (t, J = 2.5 Hz, 1H); 13C NMR (125 MHz,
CDCl3) δ 138.5, 138.3, 138.0, 138.0, 128.3, 128.3, 128.2, 127.8, 127.8, 127.7, 127.6, 127.6,
127.5, 127.5, 101.4, 84.5, 81.9, 79.0, 77.6, 75.6, 74.9, 74.8, 74.8, 74.7, 73.4, 68.7, 55.9.
Benzyl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranoside, [3i]17d: The compound 3i was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1a
(115 mg, 0.17 mmol) and benzyl alcohol acceptor 2i (0.025 ml, 0.25 mmol) in freshly dried
DCM (4 mL) in the presence of BCF (8 mg, 0.017 mmol) at ꢀ10 oC. Column chromatography
purification was performed using 7% ethyl acetate in hexane which furnished 3i as white
solid (98 mg, 92%); α:β=1:15; TLC Rf = 0.4 (10% ethyl acetate/90% hexane); 1H NMR (500
MHz, CDCl3) δ 7.30ꢀ7.16 (m, 22H), 7.08 (dd, J = 7.5, 2.0 Hz, 2H), 4.91ꢀ4.83 (m, 3H), 4.72
(dd, J = 19.0, 10.5 Hz, 2H), 4.64 (d, J = 11.0 Hz, 1H), 4.60ꢀ4.53 (m, 2H), 4.49ꢀ4.42 (m, 3H),
3.68 (dd, J = 10.5, 2.0 Hz, 1H), 3.62 (dd, J = 10.5, 5.0 Hz, 1H), 3.57ꢀ3.51 (m, 2H), 3.45 (t, J
= 8.0 Hz, 1H), 3.40ꢀ3.38 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 138.5, 138.3, 138.1, 138.0,
137.4, 128.3, 128.3, 128.3, 128.2, 128.1, 127.9, 127.8, 127.8, 127.7, 127.6, 102.5, 84.6, 82.2,
77.8, 75.6, 74.9, 74.8, 74.8, 73.4, 71.0, 68.8.
(1R,2S,5R)ꢀ2ꢀIsopropylꢀ5ꢀmethylcyclohexyl
2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀ
glucopyranoside, [3j]17e: The compound 3j was prepared using the glycosylation procedure
A: The reaction was carried out between donor 1a (71 mg, 0.15 mmol) and Lꢀmenthol
acceptor 2j (35 mg, 0.22 mmol) in freshly dried DCM (4 mL) in the presence of BCF (7 mg,
o
0.015 mmol) at ꢀ10 C. Column chromatography purification was performed using 4% ethyl
acetate in hexane which furnished 3j as White solid (71 mg, 71%); βꢀonly; TLC Rf = 0.35
1
(10% ethyl acetate/90% hexane); H NMR (500 MHz, CDCl3) δ 7.41 – 7.31 (m, 18H), 7.26ꢀ
7.25 (m, 2H), 5.00 (dd, J = 13.0, 11.0 Hz, 2H), 4.86 (dd, J = 13.0, 11.0 Hz, 2H), 4.75 (d, J =
11.0 Hz, 1H), 4.68 – 4.58 (m, 3H), 4.54 (d, J = 8.0 Hz, 1H), 3.76ꢀ3.75 (m, 2H), 3.71 – 3.64
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 24
1
2
3
4
5
6
7
8
(m, 2H), 3.59 – 3.54 (m, 1H), 3.49ꢀ3.46 (m, 2H), 2.43 – 2.40 (m, 1H), 2.20 (d, J = 12.5 Hz,
1H), 1.73ꢀ1.70 (m, 2H), 1.32 (m, 2H), 0.99 – 0.88 (m, 13H); 13C NMR (125 MHz, CDCl3) δ
138.8, 138.5, 138.3, 138.2, 128.3, 128.2, 128.2, 128.0, 127.7, 127.6, 127.6, 127.5, 127.4,
127.4, 100.7, 84.9, 82.1, 77.9, 77.7, 75.5, 74.9, 74.7, 73.6, 69.3, 48.1, 40.9, 34.4, 31.4, 25.2,
23.1, 22.2, 21.0, 15.9.
9
Cholesterol 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranoside, [3k]5c: The compound 3k was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1a
(110 mg, 0.16 mmol) and cholesterol 2k (92 mg, 0.24 mmol) in freshly dried DCM (5 mL) in
the presence of BCF (8 mg, 0.016 mmol) at ꢀ10 oC. Column chromatography purification was
performed using 5% ethyl acetate in hexane which furnished 3k as a white solid (108 mg,
75%); α:β=1:9; TLC Rf = 0.35 (8% ethyl acetate/92% hexane); 1H NMR (500 MHz, CDCl3) δ
7.40ꢀ7.29 (m, 18H), 7.22ꢀ7.21 (m, 2H), 5.38 (d, J = 5.0 Hz, 1H), 4.99 (dd, J = 28.0, 10.9 Hz,
2H), 4.84 (dd, J = 18.0, 10.5 Hz, 2H), 4.76 (d, J = 11.0 Hz, 1H), 4.65ꢀ4.53 (m, 4H), 3.76 (m,
1H), 3.70ꢀ3.59 (m, 4H), 3.50ꢀ3.48 (m, 2H), 2.48 (m, 2H), 2.07ꢀ2.05 (m, 3H), 1.91ꢀ1.89 (m,
2H), 1.61ꢀ1.33 (m, 14H), 1.21ꢀ1.11 (m, 8H), 1.07ꢀ1.05 (m, 4H), 0.96 (d, J = 6.0 Hz, 3H),
0.91 (d, J = 2.0 Hz, 3H), 0.90 (d, J = 2.0 Hz, 3H), 0.73 (s, 3H); 13C NMR (125 MHz, CDCl3)
δ 140.5, 138.6, 138.5, 138.3, 138.1, 128.3, 128.3, 128.2, 128.2, 127.9, 127.8, 127.8, 127.7,
127.6, 127.6, 127.5, 127.5, 121.9, 102.2, 84.8, 82.3, 79.6, 78.0, 75.6, 74.9, 74.9, 74.7, 73.3,
69.1, 56.7, 56.1, 50.1, 42.3, 39.7, 39.5, 39.1, 37.3, 36.7, 36.1, 35.7, 31.9, 31.8, 29.9, 29.6,
28.0, 24.2, 23.8, 22.8, 22.5, 21.0, 19.4, 18.7, 14.1, 11.8.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Ethisteroneꢀ2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranoside, [3l]: The compound 3l was
prepared using the glycosylation procedure A. To a solution of donor 1a (90 mg, 0.13 mmol)
and ethisterone 2l (37 mg, 0.12 mmol) in freshly dried DCM (4 mL), BCF (6 mg, 0.013
mmol) was added at ꢀ10 oC. Column chromatography purification was performed using 20%
ethyl acetate in hexane which furnished 3l as white solid (72 mg, 71%); α:β=1.9:1; TLC Rf =
1
0.3 (15% ethyl acetate/85% hexane); H NMR (500 MHz, CDCl3) δ 7.398ꢀ7.28 (m, 18H),
7.18ꢀ7.16 (m, 2H), 5.77 (s, 0.35H), 5.26 (d, J = 3.0 Hz, 0.65H), 5.04ꢀ4.49 (m, 8.65H), 4.08ꢀ
3.98 (m, 1.37H), 3.74ꢀ3.54 (m, 4.55H), 3.35ꢀ3.16 (m, 0.65H), 2.60ꢀ2.04 (m, 5.32H), 1.75ꢀ
1.35 (m, 9H), 1.22 (s, 3H), 1.12ꢀ0.98 (m, 2H), 0.92ꢀ0.90 (m, 5H); 13C NMR (125 MHz,
CDCl3) δ 199.6, 171.1, 139.2, 138.6, 138.4, 138.1, 137.9, 137.8, 137.7, 128.4, 128.3, 128.3,
128.3, 128.1, 128.0, 127.9, 127.9, 127.8, 127.7, 127.6, 127.6, 127.6, 123.8, 114.0, 97.4, 91.2,
87.2, 84.5, 83.1, 81.7, 79.9, 79.6, 77.7, 75.6, 75.6, 74.9, 74.7, 74.1, 73.4, 73.4, 73.2, 70.2,
68.8, 68.5, 53.3, 49.8, 46.6, 38.8, 38.5, 36.1, 35.6, 33.9, 33.7, 32.7, 32.3, 29.6, 29.6, 29.5,
29.4, 29.3, 29.1, 28.9, 23.0, 22.6, 20.6, 17.3, 14.1, 12.6; HRMS (ESIꢀTOF) m/z: [M + H]+
Calcd for C55H63O7 835.4574, found 835.4640.
ACS Paragon Plus Environment

Page 15 of 24
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranosylꢀ(1→6)ꢀ1,2:3,4ꢀdiꢀOꢀisopropylideneꢀαꢀDꢀ
galactopyranoside, [3m]17f: The compound 3m was prepared using the glycosylation
procedure B. The reaction was carried out between acceptor 2m (35 mg, 0.13 mmol) and
donor 1a (135 mg, 0.2 mmol) in freshly dried DCM (4 mL) in the presence of BCF (7 mg,
0.013 mmol) at ꢀ10 oC. Column chromatography purification was performed using 12% ethyl
acetate in hexane which furnished 3m as viscous oil (85 mg, 84%); α:β=1:8.5; TLC Rf = 0.3
(18% ethyl acetate/82% hexane); 1H NMR (500 MHz, CDCl3) δ 7.45ꢀ7.43 (m, 2H), 7.37ꢀ7.28
(m, 16H), 7.17ꢀ7.15 (m, 2H), 5.59 (d, J = 5.0 Hz, 1H), 5.08 (d, J = 11.0 Hz, 1H), 4.98 (d, J =
11.0 Hz, 1H), 4.84ꢀ4.73 (m, 3H), 4.65ꢀ4.61 (m, 2H), 4.60ꢀ4.47 (m, 3H), 4.34 (dd, J = 5.0, 2.5
Hz, 1H), 4.27 (dd, J = 8.0, 2.0 Hz, 1H), 4.18 (dd, J = 11.0, 3.5 Hz, 1H), 4.12 (dd, J = 5.5, 1.5
Hz, 1H), 3.77ꢀ3.72 (m, 3H), 3.66ꢀ3.63 (m, 2H), 3.49ꢀ3.47 (m, 2H), 1.52 (s, 3H), 1.48 (s, 3H),
1.34 (s, 3x2=6H); 13C NMR (125 MHz, CDCl3) δ 138.7, 138.1, 138.1, 128.6, 128.3, 128.3,
128.3, 128.2, 127.9, 127.8, 127.8, 127.7, 127.6, 127.5, 127.4, 109.3, 108.5, 104.4, 96.4, 84.5,
81.6, 77.7, 75.6, 74.9, 74.7, 74.3, 73.5, 71.4, 70.8, 70.5, 69.7, 68.8, 67.3, 26.0, 26.0, 25.0,
24.4.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Methyl
2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranosylꢀ(1→6)ꢀ2,3,4ꢀtriꢀOꢀbenzylꢀαꢀDꢀ
glucopyranoside, [3n]5c: The compound 3n was prepared using the glycosylation procedure
B. The reaction was carried out between acceptor 2n (80 mg, 0.17 mmol) and donor 1a (170
mg, 0.25 mmol) in freshly dried DCM (4 mL) in the presence of BCF (8 mg, 0.017 mmol) at
o
ꢀ10 C. Column chromatography purification was performed using 8% ethyl acetate in
hexane which furnished 3n as white solid (145 mg, 87%); α:β=1:4.5; TLC Rf = 0.3 (15%
ethyl acetate/85% hexane); 1H NMR (500 MHz, CDCl3) δ 7.33ꢀ7.24 (m, 29H), 7.22ꢀ7.15 (m,
6H), 4.96 (dd, J = 11.0, 4.5 Hz, 2H), 4.89 (m, 1H), 4.81ꢀ4.70 (m, 6H), 4.65ꢀ4.51 (m, 7H),
4.35ꢀ4.33 (m, 1H), 4.17 (dd, J = 11.0,2.0 Hz, 1H), 3.98 (td, J = 9.3, 5.4 Hz, 1H), 3.84ꢀ3.79
(m, 1H), 3.62ꢀ3.50 (m, 9H), 3.34 (m, 1H), 3.32 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 138.8,
138.5, 138.3, 138.3, 138.2, 138.1, 138.1, 128.4, 128.3, 128.3, 128.3, 128.1, 127.9, 127.9,
127.8, 127.8, 103.8, 98.0, 84.7, 82.0, 81.9, 79.7, 78.0, 77.9, 75.6, 75.6, 75.0, 74.9, 74.8, 73.4,
73.3, 69.8, 69.0, 68.5, 55.1.
Methyl
2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranosylꢀ(1→6)ꢀ2,3,4ꢀtriꢀOꢀbenzylꢀαꢀDꢀ
mannopyranoside, [3o]17g: The compound 3o was prepared using the glycosylation
procedure B. The reaction was carried out between acceptor 2o (65 mg, 0.14 mmol) and
donor 1a (143 mg, 0.21 mmol) in freshly dried DCM (4 mL) in the presence of BCF (7 mg,
o
0.014 mmol) at ꢀ10 C. Column chromatography purification was performed using 8% ethyl
acetate in hexane which furnished 3o as brownish solid (112 mg, 82%); α:β=1:5; TLC Rf =
1
0.35 (15% ethyl acetate/85% hexane); H NMR (500 MHz, CDCl3) δ 7.35ꢀ7.25 (m, 27H),
7.24ꢀ7.12 (m, 8H), 5.04 (d, J = 11.0 Hz, 1H), 4.94ꢀ4.90 (m, 2H), 4.80ꢀ4.76 (m, 3H), 4.70ꢀ
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 16 of 24
1
2
3
4
5
6
7
8
4.67 (m, 3H), 4.61 (d, J = 2.5 Hz, 1H), 4.59ꢀ4.58 (m, 2H), 4.54 (s, 1H), 4.52ꢀ4.51 (m, 1H),
4.49 (m, 1H), 4.40 (d, J = 8.0, 1H), 4.25 (dd, J = 10.5, 1.5 Hz, 1H), 3.93 (d, J = 9.0 Hz, 1H),
3.90ꢀ3.88 (m, 1H), 3.82ꢀ3.80 (m, 2H), 3.76ꢀ3.74 (m, 1H), 3.72ꢀ3.69 (m, 2H), 3.64ꢀ3.58 (m,
2H), 3.49 (t, J = 8.0 Hz, 1H), 3.45ꢀ3.42 (m, 1H), 3.24 (s, 3H); 13C NMR (125 MHz, CDCl3) δ
138.6, 138.5, 138.5, 138.2, 138.2, 138.2, 128.3, 128.3, 128.3, 128.2, 128.2, 128.1, 127.9,
127.8, 127.8, 127.7, 127.6, 127.5, 104.1, 98.9, 84.6, 82.1, 80.2, 77.9, 75.6, 75.0, 74.9, 74.9,
74.7, 74.6, 73.4, 72.7, 72.0, 71.4, 69.0, 54.7.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Methyl
2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranosylꢀ(1→2)ꢀ3,4,6ꢀtriꢀOꢀbenzylꢀαꢀDꢀ
mannopyranoside, [3p]: The compound 3p was prepared using the glycosylation procedure
B. The reaction was carried out between acceptor 2p (65 mg, 0.14 mmol) and donor 1a (143
mg, 0.21 mmol) in freshly dried DCM (4 mL) in the presence of BCF (8 mg, 0.014 mmol) at
ꢀ10 oC. Column chromatography purification was performed using 12% ethyl acetate/hexane
which furnished 3p as white solid (117 mg, 85%); α:β=1:9; TLC Rf = 0.35 (15% ethyl
1
acetate/85% hexane); H NMR (500 MHz, CDCl3) δ 7.38ꢀ7.20 (m, 35H), 4.88ꢀ4.86 (m, 2H),
4.84ꢀ4.79 (m, 3H), 4.76ꢀ4.69 (m, 4H), 4.63ꢀ4.57 (m, 3H), 4.49ꢀ4.44 (m, 4H), 4.34ꢀ4.29 (m,
1H), 3.89ꢀ3.83 (m, 2H), 3.78 (t, J = 3.0 Hz, 1H), 3.74ꢀ3.66 (m, 3H), 3.62ꢀ3.55 (m, 3H), 3.6
(m, 5H); 13C NMR (125 MHz, CDCl3) δ 139.4, 138.5, 138.5, 138.4, 138.4, 138.2, 128.3,
128.2, 128.2, 128.2, 128.1, 128.1, 127.8, 127.7, 127.7, 127.7, 127.7, 127.6, 127.4, 127.3,
127.3, 127.3, 102.9, 99.6, 84.8, 82.8, 78.0, 77.9, 75.8, 75.6, 75.2, 75.0, 74.8, 74.8, 73.5, 73.1,
72.8, 72.6, 71.7, 68.8, 68.7, 54.8; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C62H66O11Na
1009.4503, found 1009.4503.
Methyl
2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranosylꢀ(1→4)ꢀ2,3,6ꢀtriꢀOꢀbenzylꢀαꢀDꢀ
glucopyranoside, [3q]5c: The compound 3q was prepared using the Glycosylation Procedure
B. The reaction was carried out between acceptor 2q (58 mg, 0.13 mmol) and donor 1a (136
mg, 0.2 mmol) in freshly dried DCM (4 mL) in the presence of BCF (7 mg, 0.013 mmol) at ꢀ
10 oC. Column chromatography purification was performed using 8% ethyl acetate in hexane
which furnished 3q as semi solid (99 mg, 78%); α:β=1:2; TLC Rf = 0.3 (15% ethyl
1
acetate/85% hexane); H NMR (500 MHz, CDCl3) δ 7.43ꢀ7.39 (m, 34H), 7.14ꢀ7.12 (m, 1H),
5.05ꢀ4.70 (m, 9H), 4.64ꢀ4.52 (m, 5H), 4.45ꢀ4.40 (m, 2H), 4.12ꢀ4.07 (m, 0.60H), 3.87 (m,
2H), 3.78ꢀ3.49 (m, 8H), 3.40 (s, 3H), 3.34ꢀ3.30 (m, 0.51H); 13C NMR (125 MHz, CDCl3) δ
138.6, 138.6, 138.5, 138.5, 138.3, 138.3, 138.2, 137.8, 128.4, 128.4, 128.4, 128.4, 128.3,
128.3, 128.2, 128.1, 128.0, 128.0, 127.9, 127.8, 127.8, 127.8, 127.7, 127.7, 127.7, 127.6,
127.6, 127.5, 127.3, 127.2, 127.1, 126.7, 102.5, 99.3, 98.4, 97.7, 96.6, 84.8, 84.6, 82.8, 82.2,
82.0, 80.4, 80.2, 79.5, 78.8, 78.0, 75.1, 75.0, 75.0, 74.9, 74.8, 74.6, 73.6, 73.4, 73.3, 73.2,
73.1, 72.3, 71.0, 70.0, 69.5, 69.0, 68.9, 67.8, 55.3, 55.1.
ACS Paragon Plus Environment

Page 17 of 24
The Journal of Organic Chemistry
1
2
Methyl
2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranosylꢀ(1→4)ꢀ2,3ꢀdiꢀOꢀbenzoylꢀ6ꢀOꢀ
3
4
5
6
7
8
9
benzylꢀαꢀDꢀglucopyranoside, [3r]: The compound 3r was prepared using the glycosylation
procedure B. The reaction was carried out between acceptor 2r (35 mg, 0.07 mmol) and
donor 1a (70 mg, 0.11 mmol) in freshly dried DCM (4 mL) in the presence of BCF (5 mg,
0.007 mmol) at ꢀ10 oC. Column chromatography purification was performed using 15% ethyl
acetate in hexane which furnished 3r as semi solid (58 mg, 82%); α:β=1:2; TLC Rf = 0.3
(20% ethyl acetate/80% hexane); 1H NMR (500 MHz, CDCl3) δ 8.00ꢀ7.91 (m, 4H), 7.52ꢀ7.46
(m, 3H), 7.43ꢀ7.28 (m, 25H), 7.21ꢀ7.09 (m, 8H), 5.17ꢀ5.16 (m, 2H), 5.10 (d, J = 11.0 Hz,
1H), 5.06ꢀ5.02 (m, 1H), 4.96 (d, J = 10.5 Hz, 1H), 4.86ꢀ4.84 (m, 3H), 4.63ꢀ4.57 (m, 3H),
4.50ꢀ4.48 (m, 2H), 4.48 (m, 1H), 4.28 (dd, J = 11.0, 2.0 Hz, 1H), 4.08ꢀ3.95 (m, 2H), 3.90ꢀ
3.87 (m, 1H), 3.83ꢀ3.79 (m, 1H), 3.77ꢀ3.74 (m, 1H), 3.73ꢀ3.70 (m, 1H), 3.69ꢀ3.66 (m, 1H),
3.64 (m, 1H), 3.58 (t, J = 8.0 Hz, 1H), 3.50ꢀ3.45 (m, 1H), 3.39 (s, 1H), 3.38 (s, 2H); 13C
NMR (125 MHz, CDCl3) δ 166.0, 165.6, 165.6, 165.6, 138.4, 138.1, 133.2, 129.9, 129.7,
129.6, 129.18, 128.4, 128.3, 128.3, 128.3, 128.2, 128.0, 127.9, 127.9, 127.8, 127.7, 127.7,
127.6, 127.5, 103.9, 96.9, 84.7, 82.1, 77.9, 77.6, 77.2, 76.5, 75.8, 75.7, 75.5, 75.0, 75.0, 74.8,
74.6, 74.4, 73.4, 72.7, 72.6, 72.3, 69.7, 68.9, 68.2, 55.3; HRMS (ESIꢀTOF) m/z: [M + H]+
Calcd for C62H63O13 1015.4269, found 1015.4222.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Methyl
2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranosylꢀ(1→3)ꢀ4,6ꢀOꢀbenzylideneꢀαꢀDꢀ
Methyl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranosylꢀ
glucopyranoside [3sa]17h and
(1→2)ꢀ4,6ꢀOꢀbenzylideneꢀαꢀDꢀglucopyranoside [3sb]17h: The compound 3sa and 3sb was
prepared using the glycosylation procedure B. To a solution of donor 1a (120 mg, 0.18
mmol) and acceptor 2s (72 mg, 0.27 mmol) in freshly dried DCM (5 mL), BCF (10 mg, 0.018
o
mmol) was added at ꢀ10 C. Column chromatography purification furnished 3sa and 3sb.
Data for 3sa: Yellowish Solid (75 mg, 51%); α:β=1:3.5; TLC Rf = 0.5 (17% ethyl
1
acetate/83% hexane); H NMR (500 MHz, CDCl3) δ 7.53ꢀ7.51 (m, 2H), 7.39ꢀ7.29 (m, 21H),
7.20ꢀ7.18 (m, 2H), 5.56 (s, 1H), 5.00ꢀ4.92 (m, 3H), 4.84ꢀ4.79 (m, 4H), 4.69 (d, J = 8.0 Hz,
1H), 4.58ꢀ4.55 (m, 2H), 4.53ꢀ4.49 (m, 1H), 4.32 (dd, J = 10.0, 5.0 Hz, 1H), 4.21 (t, J = 9.0
Hz, 1H), 3.92ꢀ3.86 (m, 1H), 3.76 (m, 1H), 3.71ꢀ3.65 (m, 4H), 3.61ꢀ3.55 (m, 3H), 3.53ꢀ3.49
(m, 1H), 3.45ꢀ3.43 (each s, (0.65 and 2.19 H) 3H); 13C NMR (125 MHz, CDCl3) δ 138.4,
138.1, 137.9, 137.9, 137.1, 129.1, 128.4, 128.4, 128.3, 128.3, 128.2, 127.9, 127.9, 127.9,
127.8, 127.7, 127.7, 127.6, 127.6, 126.3, 104.6, 102.0, 100.2, 84.8, 81.8, 81.7, 81.4, 77.7,
75.6, 74.9, 74.9, 74.7, 73.4, 69.6, 69.1, 62.0, 55.4; HRMS: Calcd for C48H53O11 [M+H]+:
805.3588; found: 805.3526. Data for 3sb. White solid (42 mg, 29%); α:β=1:7; TLC Rf = 0.3
1
(17% ethyl acetate/83% hexane); H NMR (500 MHz, CDCl3) δ 7.50 (dd, J = 8.0, 2.5 Hz,
2H), 7.35ꢀ7.28 (m, 20H), 7.16ꢀ7.15 (m, 3H), 5.54 (s, 1H), 4.93ꢀ4.86 (m, 4H), 4.79ꢀ4.73 (m,
3H), 4.56 (d, J = 2.0 Hz, 1H), 4.54 (d, J = 3.5 Hz, 1H), 4.42 (d, J = 12.0 Hz, 1H), 4.28 (dd, J
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 24
1
2
3
4
5
6
7
8
= 10.0, 5.0 Hz, 1H), 4.10 (t, J = 9.0 Hz, 1H), 3.88ꢀ3.84 (m, 1H), 3.76 (t, J = 10.0 Hz, 1H),
3.68ꢀ3.50 (m, 8H), 3.45ꢀ3.40 (m, 4H);13C NMR (125 MHz, CDCl3) δ 138.2, 138.2, 137.9,
137.7, 137.3, 128.8, 128.4, 128.3, 128.2, 128.0, 128.0, 127.9, 127.9, 127.8, 127.8, 127.8,
127.7, 127.6, 127.5, 127.3, 126.4, 126.2, 103.2, 101.4, 99.8, 85.1, 82.1, 80.7, 79.0, 77.9, 75.5,
75.2, 75.0, 74.9, 73.6, 72.6, 68.9, 68.8, 62.8, 55.3.
9
2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀglucopyranosylꢀ(1→3)ꢀ1,2:5,6ꢀdiꢀOꢀisopropylideneꢀαꢀDꢀ
glucofuranoside, [3t]6c: The compound 3t was prepared using the glycosylation procedure B.
The reaction was carried out between acceptor 2t (40 mg, 0.15 mmol) and donor 1a (157 mg,
0.23 mmol) in freshly dried DCM (4 mL) in the presence of BCF (8 mg, 0.015 mmol) at ꢀ10
oC. Column chromatography purification was performed using 12% ethylacetate in hexane
which furnished 3t as white solid (84 mg, 72%); α:β=5.5:1; TLC Rf = 0.25 (15% ethyl
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
acetate/85% hexane); H NMR (500 MHz, CDCl3) δ 7.36ꢀ7.28 (m, 17H), 7.23ꢀ7.15 (m, 3H),
5.91 (d, J = 3.5 Hz, 1H), 5.27 (d, J = 3.5 Hz, 1H), 5.00ꢀ4.82 (m, 4H), 4.76ꢀ4.70 (m, 3H),
4.64ꢀ4.48 (m, 5H), 4.25 (d, J = 2.0 Hz, 1H), 4.17ꢀ4.15 (m, 1H), 4.07 (d, J = 5.5 Hz, 1H), 3.96
(t, J = 9.0 Hz, 1H), 3.82 (d, J = 10.0 Hz, 1H), 3.74 (m, 2H), 3.65ꢀ3.60 (m, 2H), 1.51 (s, 3H),
1.44 (s, 3H), 1.28 (s, 3H), 1.25 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 138.5, 138.0, 137.9,
137.7, 128.4, 128.3, 128.3, 128.3, 128.0, 127.9, 127.8, 127.5, 111.8, 109.0, 105.1, 97.9, 83.6,
81.4, 81.1, 80.7, 79.9, 77.7, 75.6, 75.2, 73.5, 73.0, 72.3, 71.2, 68.6, 66.9, 26.9, 26.7, 26.0,
25.4.
2ꢀPropyl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀgalactopyranoside, [3u]5c: The compound 3u was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1c
(100 mg, 0.15 mmol) and isoꢀpropanol 2a (0.017 ml, 0.23 mmol) in freshly dried DCM (4
o
mL) in the presence of BCF (8 mg, 0.015 mmol) at ꢀ10 C. Column chromatography
purification was performed using 7% ethyl acetate in hexane which furnished 3u as white
1
solid (73 mg, 84%); TLC Rf = 0.35 (10% ethyl acetate/90% hexane); H NMR (500 MHz,
CDCl3) δ 7.41ꢀ7.31 (m, 20H), 5.01ꢀ4.98 (m, 2H), 4.82ꢀ4.74 (m, 3H), 4.67 (d, J = 12.0 Hz,
1H), 4.51ꢀ4.45 (m, 3H), 4.05ꢀ4.03 (m, 1H), 3.93 (d, J = 2.5 Hz, 1H), 3.85 (dd, J = 9.5, 7.5
Hz, 1H), 3.64ꢀ3.55 (m, 4H), 1.33 (d, J = 6.0 Hz, 3H), 1.27 (d, J = 6.5 Hz, 3H); 13C NMR (125
MHz, CDCl3) δ 138.8, 138.6, 138.5, 137.9, 128.3, 128.3, 128.2, 128.2, 128.2, 128.1, 128.0,
127.8, 127.4, 127.4, 102.4, 82.3, 79.5, 75.1, 74.4, 73.5, 73.4, 73.3, 73.0, 72.0, 69.0, 23.6,
22.0.
Propyl 2,3,4,6ꢀtetraꢀOꢀbenzylꢀβ,αꢀDꢀmannopyranoside, [3v]17i: The compound 3v was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1d
(116 mg, 0.17 mmol) and isoꢀpropanol acceptor 2a (0.019 ml, 0.25 mmol) in freshly dried
DCM (4 mL) in the presence of BCF (9 mg, 0.017 mmol) at ꢀ10 oC. Column chromatography
purification was performed using 7% ethyl acetate in hexane which furnished 3v as white
ACS Paragon Plus Environment

Page 19 of 24
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
1
solid (91 mg, 92%). TLC Rf = 0.35 (10% ethyl acetate/90% hexane); H NMR (500 MHz,
CDCl3) δ 7.52 (d, J = 6.5 Hz, 2H), 7.41ꢀ7.32 (m, 16H), 7.31ꢀ7.23 (m, 2H), 5.05ꢀ5.03 (m, 1H),
4.96ꢀ4.92 (m, 1.72H), 4.82 (d, J = 12.0 Hz, 0.23H), 4.75 (d, J = 12.0 Hz, 0.23H), 4.71 (d, J =
12.0 Hz, 0.24H), 4.67ꢀ4.64 (m, 1.76H), 4.59ꢀ4.54 (m, 2H), 4.50ꢀ4.46 (m, 1.46H), 4.06 (m,
1H), 3.89ꢀ3.84 (m, 3H), 3.79ꢀ3.77 (m, 1.22H), 3.54 (dd, J = 9.3, 3.0 Hz, 0.72H), 3.50ꢀ3.47
(m, 0.73H), 1.34 (d, J = 6.0 Hz, 3H), 1.20 (dd, J = 6.5, 3H); 13C NMR (125 MHz, CDCl3) δ
138.8, 138.4, 138.4, 138.3, 138.2, 128.4, 128.2, 128.2, 128.0, 127.9, 127.7, 127.7, 127.5,
127.5, 127.5, 127.4, 99.5, 95.7, 82.5, 80.3, 75.8, 75.2, 75.1, 75.1, 75.0, 74.9, 74.0, 73.7, 73.3,
73.2, 72.6, 72.1, 71.6, 71.3, 71.1, 69.8, 69.2, 68.8, 23.6, 21.7.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Butyl 2ꢀOꢀbenzoylꢀ3,4,6ꢀtriꢀOꢀbenzylꢀβꢀDꢀglucopyranoside, [4a]: The compound 4a was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1f
(100 mg, 0.14 mmol) and nꢀbutanol 2c (0.019 ml, 0.21 mmol) in freshly dried DCM (4 mL)
in the presence of BCF (7 mg, 0.014 mmol) at ꢀ10 oC. The reaction was further stirred for 30
minutes at this temperature. Column chromatography purification was performed using 7%
ethyl acetate/hexane which furnished 4a as white solid (74 mg, 87%); TLC Rf = 0.45 (20%
ethyl acetate/80% hexane); 1H NMR (500 MHz, CDCl3) δ 8.04 (dd, J = 8.0, 1.0 Hz, 2H), 7.59
(t, J = 7.5, 1H), 7.46 (t, J = 7.5 Hz, 2H), 7.40ꢀ7.31 (m, 8H), 7.22 (dd, J = 7.5, 2.0 Hz, 2H),
7.16 (m, 5H), 5.30 (dd, J = 9.0, 8.0 Hz, 1H), 4.85 (d, J = 11.0 Hz, 1H), 4.77 (d, J = 11.0 Hz,
1H), 4.71ꢀ4.66 (m, 2H), 4.63ꢀ4.60 (m, 2H), 4.53 (d, J = 8.0 Hz, 1H), 3.91ꢀ3.76 (m, 5H), 3.61ꢀ
3.57 (m, 1H), 3.51ꢀ3.46 (m, 1H), 1.45 (m, 2H), 1.24 (m, 2H), 0.75 (t, J = 7.5 Hz, 3H); 13C
NMR (125 MHz, CDCl3) δ 165.1, 138.1, 137.9, 137.8, 132.9, 130.0, 129.6, 128.3, 128.3,
128.2, 128.2, 127.9, 127.9, 127.8, 127.7, 127.5, 101.1, 82.7, 78.0, 75.2, 75.0, 74.9, 73.8, 73.4,
69.4, 68.8, 31.4, 18.8, 13.5; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C38H42O7Na
633.2828, found 633.2877.
Cyclohexyl 2ꢀOꢀbenzoylꢀ3,4,6ꢀtriꢀOꢀbenzylꢀβꢀDꢀglucopyranoside, [4b]17j: The compound
4b was prepared using the glycosylation procedure A. The reaction was carried out between
donor 1f (125 mg, 0.18 mmol) and cyclohexanol acceptor 2s (0.028 ml, 0.27 mmol) in freshly
o
dried DCM (4 mL) in the presence of BCF (9 mg, 0.018 mmol) at ꢀ10 C. Column
chromatography purification was performed using 7% ethyl acetate in hexane which
furnished 4b as white solid (104 mg, 91%). TLC Rf = 0.45 (20% ethyl acetate/80% hexane);
1H NMR (500 MHz, CDCl3) δ 8.04ꢀ8.03 (m, 2H), 7.59 (t, J = 7.5 Hz, 1H), 7.46 (t, J = 8.0 Hz,
2H), 7.39ꢀ7.28 (m, 8H), 7.24ꢀ7.22 (m, 2H), 7.17ꢀ7.14 (m, 5H), 5.27 (t, J = 9.0 Hz, 1H), 4.85
(d, J = 11.0 Hz, 1H), 4.76 (d, J = 11.5 Hz, 1H), 4.69ꢀ4.60 (m, 5H), 3.84ꢀ3.80 (m, 2H), 3.76ꢀ
3.72 (m, 2H), 3.67 (m, 2H), 1.90ꢀ1.88 (m, 1H), 1.68 (m, 2H), 1.57ꢀ1.55 (m, 1H), 1.45ꢀ1.42
(m, 2H), 1.23 (m, 2H), 1.15ꢀ1.13 (m, 2H); 13C NMR (125 MHz, CDCl3) δ 165.1, 138.2,
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 20 of 24
1
2
3
4
5
6
7
8
137.9, 137.8, 132.8, 130.2, 129.6, 128.4, 128.3, 128.3, 128.2, 128.0, 128.0, 127.8, 127.7,
127.5, 99.6, 82.8, 78.1, 77.5, 75.2, 75.0, 74.9, 74.01, 73.4, 68.9, 33.2, 31.5, 25.4, 23.7, 23.4.
Butyl 2ꢀOꢀbenzoylꢀ3,4,6ꢀtriꢀOꢀbenzylꢀαꢀDꢀmannopyranoside, [4c]: The compound 4c was
prepared using the glycosylation procedure A. The reaction was carried out between donor 1g
(150 mg, 0.21 mmol) and nꢀbutanol 2c (0.027 ml, 0.32 mmol) in freshly dried DCM (4 mL)
in the presence of BCF (11 mg, 0.021 mmol) at ꢀ10 oC. Column chromatography purification
was performed using 7% ethyl acetatein hexane which furnished 4c as viscous oil (117 mg,
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
92%); TLC Rf = 0.55 (20% ethyl acetate/85% hexane); H NMR (500 MHz, CDCl3) δ 8.09
(dd, J = 8.5, 1.5 Hz, 2H), 7.57 (t, J = 7.5 Hz, 1H), 7.41ꢀ7.20 (m, 17H), 5.63 (t, J = 2.5 Hz,
1H), 4.97 (d, J = 2.0 Hz, 1H), 4.89 (d, J = 10.5 Hz, 1H), 4.82 (d, J = 11.0 Hz, 1H), 4.76 (d, J
= 12.0 Hz, 1H), 4.61ꢀ4.54 (m, 3H), 4.13ꢀ4.10 (m, 2H), 3.91 (m, 2H), 3.80 (dd, J = 10.0, 1.5
Hz, 1H), 3.76ꢀ3.71 (m, 1H), 3.49ꢀ3.45 (m, 1H), 1.59ꢀ1.58 (m, 2H), 1.43ꢀ1.36 (m, 2H), 0.94 (t,
J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 165.7, 138.4, 138.3, 138.0, 133.0, 129.9,
128.3, 128.3, 128.2, 128.0, 128.0, 127.6, 127.5, 127.5, 127.4, 97.7, 78.3, 75.3, 74.4, 73.4,
71.5, 71.5, 69.1, 69.0, 67.7, 31.4, 19.3, 13.8. HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for
C38H42O7Na 633.2828, found 633.2877.
Cyclohexyl
2ꢀOꢀbenzoylꢀ3,4,6ꢀtriꢀOꢀbenzylꢀαꢀDꢀmannopyranoside,
[4d]17k
:
The
compound 4d was prepared using the glycosylation procedure A. The reaction was carried
out between donor 1g (110 mg, 0.16 mmol) and cyclohexanol acceptor 2s (0.025 ml, 0.24
o
mmol) in freshly dried DCM (4 mL) in the presence of BCF (8 mg, 0.016 mmol) at ꢀ10 C.
Column chromatography purification was performed using 7% ethyl acetate in hexane which
furnished 4d as viscous oil (86 mg, 85%); TLC Rf = 0.55 (20% ethyl acetate/80% hexane); 1H
NMR (500 MHz, CDCl3) δ 8.10ꢀ8.09 (m, 2H), 7.57 (t, J = 7.5 Hz, 1H), 7.41ꢀ7.21 (m, 16H),
5.59ꢀ5.58 (m, 1H), 5.13 (d, J = 1.5 Hz, 1H), 4.89 (d, J = 11.0 Hz, 1H), 4.83 (d, J = 11.0 Hz,
1H), 4.76 (d, J = 12.0 Hz, 1H), 4.61ꢀ4.54 (m, 3H), 4.16ꢀ4.11 (m, 2H), 3.94ꢀ3.91 (m, 2H),
3.80 (dd, J = 10.5, 1.5 Hz, 1H), 3.68ꢀ3.64 (m, 1H), 1.88 (m, 2H), 1.73ꢀ1.72 (m, 2H), 1.53ꢀ
1.52 (d, J = 5.2 Hz, 1H), 1.41ꢀ1.38 (m, 1H), 1.33 (m, 1H), 1.31 (s, 1H), 1.26ꢀ1.24 (m, 2H).
13C NMR (125 MHz, CDCl3) δ 165.8, 138.5, 138.3, 138.1, 133.0, 130.0, 129.9, 128.3, 128.3,
128.3, 128.2, 128.0, 128.0, 127.6, 127.5, 127.4, 127.4, 95.8, 78.3, 75.3, 74.5, 73.3, 71.5, 71.5,
69.7, 69.1, 33.2, 31.3, 25.5, 24.0, 23.7.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website.
Copies of H NMR of isoꢀpropanol in the presence of and absence of B(C6F5)3 and 1H and 13C
1
NMR of glycoside 3aꢀ3v and 4aꢀ4d.
ACS Paragon Plus Environment

Page 21 of 24
The Journal of Organic Chemistry
1
2
AUTHOR INFORMATION
3
4
Corresponding Author
5
6
Email: jeyakumar.chy@iitbhu.ac.in
7
8
9
NOTES
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The authors declare no competing financial interest
ACKNOWLEDGEMENT
J. K. acknowledges MaxꢀPlanck SocietyꢀGermany and DSTꢀIndia (DST/INT/MPG/Pꢀ
09/2016) for financial support through IndoꢀMax Planck partner group project. J. K. also
acknowledges DSTꢀSERB for the young scientist start up research grant (YSS/2014/000236).
KBM sincerely thanks DSTꢀSERB, Department of Science & Technology, New Delhi for
National Post Doctoral Fellowship scheme (File no NPDF/2016/001709). A. K. S.
acknowledges the CSIR for senior research fellowship (SRF). J. K acknowledges Central
Instrumentation Facility Center (CIFC)ꢀIIT BHU for the NMR facilities and MASS facilities.
We thank Mr. Albert for editing the manuscript.
REFERENCES
1) (a) Varki, A. Essentials of Glycobiology, Cold Spring Harbor Laboratory Press, New York
(USA), 1999. (b) Lindhorst, T. K. Essentials of Carbohydrate Chemistry and Biochemistry,
WILEYꢀVCH Verlag GmbH & Co. KGaA, Weinheim, 2008. (c) Seeberger, P. H.; Werz, D.
B. Nature, 2007, 446, 1046; (d) Seeberger, P. H.; Werz, D. B. Nat. Rev. Drug Discov., 2005,
4, 751.
2) (a) Bennett, C. S. Selective Glycosylations: Synthetic Methods and Catalysts, WileyꢀVCH
Verlag GmbH & Co. KGaA, 2017. (b) Werz, D. B.; Vidal, S. Modern Synthetic Methods in
Carbohydrate Chemistry: From Monosaccharides to Complex Glycoconjugates, WileyꢀVCH
Verlag GmbH & Co. KGaA, 2014. (c) Khan, S. H. Modern Methods in Carbohydrate
Synthesis, CRC Press, Taylor & Francis Group, 1996.
3) (a) Jung, K.ꢀH.; Müller, M.; Schmidt, R. R. Chem. Rev., 2000, 100, 4423. (b) Zhu, X.;
Schmidt, R. R. Angew. Chem., Int. Ed. 2009, 48, 1900. (c) Demchenko, A. V. Handbook of
Chemical Glycosylation: Advances in Stereoselectivity and Therapeutic Relevance, Wileyꢀ
VCH Verlag GmbH & Co. KGaA, 2008. (d) Ishiwata, A.; Lee Y. J.; Ito, Y. Org. Biomol.
Chem., 2010, 8, 3596. (e) Schumann, B.; Parameswarappa, S. G.; Lisboa, M. P.; Kottari, N.;
Guidetti, F.; Pereira, C. L.; Seeberger, P. H. Angew. Chem. Int. Ed. Engl., 2016, 55, 14429.
4) Ranade, S. C.; Demchenko, A. V. J. Carbohydr.Chem., 2013, 32, 1.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 22 of 24
1
2
3
4
5
6
7
8
5) (a) Peng, P.; Schmidt, R. R. Acc. Chem. Res., 2017, 50, 1171. (b) Peng, P.; Schmidt, R. R.
J. Am. Chem. Soc., 2015, 137, 12653. (c) Kumar, A.; Geng Y. Q.; Schmidt, R. R. Adv. Synth.
Catal., 2012, 354, 1489. (d) Kumar, A.; Kumar, V.; Dere R. T.; Schmidt, R. R. Org. Lett.,
2011, 13, 3612. (e) Geng, Y.; Kumar, A.; Faidallah, H. M.; Albar, H. A.; Mhkalid, I. A.;
Schmidt, R. R. Angew. Chem., Int. Ed., 2013, 52, 10089.
9
6) (a) Schmidt, R. R. and Michel, J. Angew. Chem. Int. Ed. Engl., 1980, 19, 731. (b) Fraserꢀ
Reid, B. O.; Tatsuta K.; J. Thiem, Glycoscience: Chemistry and Chemical Biology, Springerꢀ
Verlag, New York, 2008. (c) Schmidt, R. R.; Michel, J.; J. Carbohydr. Chem.,1985, 4, 141.
7) (a) Li X. H.; Zhu, J. L. Eur. J. Org. Chem., 2016, 4724. (b) McKay M. J.; Nguyen, H. M.
ACS Catal., 2012, 2, 1563. (c) Williams, R.; Galan, M. C. Eur. J. Org. Chem., 2017, 6247.
8) Yang, J. M.; CooperꢀVanosdell, C.; Mensah, E. A.; Nguyen, H. M. J. Org. Chem., 2008,
73, 794.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
9) Medina, S.; Henderson, A. S.; Bower, J. F.; Galan, M. C. Chem. Commun., 2015, 51,
8939.
10) (a) Kimura, T.; Eto, T.; Takahashi D.; Toshima, K. Org. Lett., 2016, 18, 3190. (b) Cox,
D. J.; Smith, M. D.; Fairbanks, A. J. Org. Lett., 2010, 12, 1452.
11) Kowalska, K.; Pedersen, C. M. Chem. Commun., 2017, 53, 2040.
12) (a) Kargbo, R. B. Synlett, 2004, 1118. (b) Rubin, M.; Gevorgyan, V.; Chandrasekhar, S.;
Nagendra Babu, B.; Chandrashekar, G.; eꢀEROS Encyclopedia of Reagents for Organic
Synthesis, 2009. (c) Chandrasekhar, S.; Babu, B. N.; Chandrashekar, G. eꢀEROS
Encyclopedia of Reagents for Organic Synthesis, 2006.
13) Lawson, J. R.; Melene, R. L. Inorg. Chem., 2017, 56, 8627ꢀ8643.
14) (a) Chandrasekhar, S.; Reddy, C. R.; Chandrashekar, G. Tetrahedron Lett., 2004, 45,
6481. (b) Bender, T. A.; Dabrowski, J. A.; Zhong, H. Y.; Gagne, M. R. Org. Lett., 2016, 18,
4120. (c) Adduci, L. L.; Bender, T. A.; Dabrowski, J. A.; Gagne, M. R. Nat. Chem., 2015, 7,
759. (d) Adduci, L. L.; McLaughlin, M. P.; Bender, T. A.; Becker, J. J.; Gagne, M. R.
Angew. Chem. Int. Ed. Engl., 2014, 53, 1646.
15) (a) Karimov, R. R.; Tan, D. S.; Gin, D. Y. Chem. Commun., 2017, 53, 5838. (b) Wang,
P.; Kim, YꢀJ.; NavarroꢀVillalobos, M.; Rohde, B. D.; Gin, D. Y. J. Am. Chem. Soc., 2005,
127, 3256.
16) (a) Mbadugha, B. N. A.; Menger, F. M. Org. Lett., 2003, 5, 4041; (b) Kumar, D.;
Mishra, K. B.; Mishra, B. B.; Mondal, S.; Tiwari, V. K. Steroids, 2014, 80, 71. (c) Munafo,
J. P.; Gianfagna, T. J. Nat. Prod. Rep., 2015, 32, 454.
17) (a) Garcia, B. A.; Gin, D. Y. J. Am. Chem. Soc., 2000, 122, 4269. (b) Hoang, K. L. M.;
Bai, Y.; Ge, X.; Liu, XꢀW. J. Org. Chem., 2013, 78, 5196–5204. (c) Higashi, K.; Susaki,
H. Chem. Pharm. Bull., 1992, 40, 2019. (d) Lu, W.; Navidpour, L.; Taylor, S. D. Carbohydr.
ACS Paragon Plus Environment

Page 23 of 24
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
Res., 2005, 340, 1213. (e) Imagawa, H.; Kinoshita, A.; Fukuyama, T.; Yamamoto, H.;
Nishizawa, M. Tetrahedron Lett., 2006, 47, 4729. (f) Vankar, Y.D.; Vankar, P.S.; Behrendt,
M.; Schmidt, R.R. Tetrahedron, 1991, 47, 9985. (g) He, H.; Zhu, X. Org. Lett., 2014, 16,
3102. (h) FraserꢀReid, B.; Lopez, J. C.; Radhakrishnan, K. V.; Mach, M.; Schlueter, U.;
Gomez, A.; Uriel, C. Can. J. Chem., 2002, 80, 1075. (i) Koppolu, S. R.; Niddanaa, R.;
Balamurugan, R. Org. Biomol. Chem., 2015, 13, 5094–5097. (j) Heuckendorff, M.;
Premathilake, H. D.; Pornsuriyasak, P.; Madsen, A. Ø.; Pedersen, C. M.; Bols M.;
Demchenko, A. V. Org. Lett., 2013, 15, 4904–4907. (k) Saithalavi, A.; Sanjayan, S. V.;
Rani, R.; Thirumalai, K. R.; Vasu, R. K. Bull. Chem. Soc. Jpn., 2007, 80, 553.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 24 of 24
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment