Selective Palladium-Catalyzed Domino Heck/Buchwald–Hartwig Arylations of N-Glycosylcinnamamides: An Efficient Route to 4-Aryl-N-glycosylquinolin-2-ones

Article abstract of DOI:10.1002/adsc.201601382

An efficient and selective domino Heck/Buchwald–Hartwig arylations of readily available N-glycosylcinnamamides with aryl iodides have been established. Using palladium(II) acetate as a catalyst, potassium acetate as the base and tetrabutylamonium bromide as an additive in dioxane, the protocol proved to be general, and a variety of 4-aryl-N-glycosylquinolin-2-ones has been prepared in good yields with exclusive α- or β-selectivity. (Figure presented.).

Full text of DOI:10.1002/adsc.201601382

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DOI: 10.1002/adsc.201601382
Selective Palladium-Catalyzed Domino Heck/Buchwald–Hartwig
Arylations of N-Glycosylcinnamamides: An Efficient Route to 4-
Aryl-N-glycosylquinolin-2-ones
Thi Thanh Huyen Luong,a Sabrina Touchet,a Mouad Alami,a
and Samir Messaoudia,*
a
Univ Paris-Sud, CNRS, BioCIS-UMR 8076, Equipe Labellisꢀe Ligue Contre le Cancer, Laboratoire de Chimie
Thꢀrapeutique, Facultꢀ de Pharmacie, 5 rue J.-B. Clꢀment, 92296 Chꢁtenay-Malabry, France
Fax : (+33)-146-83-58-87; e-mail: samir.messaoudi@u-psud.fr
Received: December 16, 2016; Revised: February 10, 2017; Published online: && &&, 0000
Supporting information for this article is available under http://dx.doi.org/10.1002/adsc.201601382.
Abstract: An efficient and selective domino Heck/ sylquinolin-2-ones has been prepared in good yields
Buchwald–Hartwig arylations of readily available N- with exclusive a- or b-selectivity.
glycosylcinnamamides with aryl iodides have been
established. Using palladium(II) acetate as a catalyst,
potassium acetate as the base and tetrabutylamoni- Keywords: 4-aryl-N-glycosylquinolin-2-ones; Heck/
um bromide as an additive in dioxane, the protocol Buchwald–Hartwig reactions; N-glycosylcinnam-
proved to be general, and a variety of 4-aryl-N-glyco-
ACHTUNGTNERaNUNG mides; palladium catalysis
Introduction
Heteroaryl-N-glycosides are of high importance in
medicinal chemistry and commonly found in many
compounds of enormous practical importance, rang-
ing from natural compounds to pharmaceutical
agents[1] (Figure 1). Although this family of glycosides
possesses a great potential in medicinal chemistry,
only few efforts have been dedicated to the develop-
ment of efficient methodologies to access to heteroar-
yl-N-glycosides with a perfect control of the a- or b-
configuration, probably due to the difficulty to intro-
duce stereoselectively a nitrogen aglycone at the
anomeric position of a sugar moiety.[2] Thus, there is
a strong impetus to discover new chemical transfor-
mations for the efficient synthesis of heteroaryl-N-gly-
cosides. One of the most important subfamilies of het-
eroaryl-N-glycosides is N-glycosylquinolin-2-ones in
which a glycosyl unit is attached to a quinolin-2-one
core. Quinolin-2-(1H)-ones are present in many bio-
logically active compounds and pharmaceutical
agents.[3] The attachment of N-glycosyl units to a qui-
nolin-2-one nucleus can cause several changes in their
features, including their chemical, physical, and bio-
chemical properties such as oral absorption and bio-
availability. Moreover, the sugar nucleus has been in-
creasingly used to address issues that are commonly Figure 1. Heteroaryl-N-glycoside-based bioactive molecules.
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encountered in the process of drug discovery such as cinnamamides of type E-2 could be utilized as a build-
ADMET parameters.[4]
ing block in the synthesis of 4-aryl-N-glycosylquino-
Thus, developing a simple method for the synthesis lin-2-ones through Pd(0)-catalyzed domino Heck/
of substituted N-glycosylquinolin-2-ones would be of Buchwald–Hartwig arylation reactions [Scheme 1, Eq.
great interest for the preparation of large libraries of (3)]. The Heck reaction should produce the tri-substi-
new potentially active compounds. This reaction tuted vinylic intermediate in which the geometry of
should allow the introduction of new units having var- the double bond is isomerized from E- to Z-configu-
ious chemical functions on the quinolin-2-one scaffold ration.
efficiently within a minimum of steps. The most suita-
ble method able to address this challenge is (auto)tan-
dem catalysis.[5] These processes which use a single Results and Discussion
precatalyst to effect two or more mechanistically dis-
tinct catalytic cycles in a single reaction vessel are rec- To achieve successfully our goal, initial investigations
ognized as a powerful tool in several areas of organic focused on identifying optimal conditions for the cou-
chemistry. This approach has emerged as an atom- pling of N-glycosylcinnamamide E-2a with the 4-io-
economic strategy not only because of a reduction in doanisole 1a as the model study (Table 1). To our sur-
workload, waste and energy consumption, but also prise, heating the mixture of 2a and 1a (1.5 equiv.)
the synthesis of complex products that are otherwise under Cacchiꢃs[5m] conditions [Pd(OAc)2 (5 mol%),
difficult to obtain through a classical multistep synthe- tetrabutylamonium acetate (3 equiv.), tetrabutylamo-
ses.
nium bromide (3 equiv.) in dioxane at 1308C for 24 h]
Recently, our group reported an efficient protocol led to N-b-glycosylquinolin-2-one 3a (J1,2 =9.9 Hz) in
for the synthesis of N-glycosylquinolin-2-ones 45% yield (entry 1, Table 1). Increasing the reaction
(Scheme 1) via a palladium-catalyzed intramolecular time up to 48 h led to a slightly better yield of 3a
N-arylation of various substituted (2-iodophenyl)-Z- (52%, entry 2) however, when the reaction mixture
acrylamido sugars Z-2 [Eq. (1)].[6] During this study, was heated at 1308C for a longer time (60 h), the
we showed that the Z-configuration of the double yield dropped to 35% (entry 3) probably due to deg-
bond plays a critical role in the outcome of the reac- radation of the starting materials and product. En-
tion since trans-acrylamido sugars E-2 could never couraged by these preliminary results, we further in-
been reacted under our reaction conditions vestigated the reaction parameters and found that the
[Scheme 1, Eq. (2)].
efficiency of the reaction was significantly affected by
As part of our continuing efforts to functionalize the amount of 1a used and the choice of the base. We
sugars under transition metal catalysis to access com- were delighted to find that the use of KOAc as the
plex glycosides,[7] we considered whether N-glycosyl- base in combination with Pd(OAc)2 for 48 h heating
Scheme 1. Synthesis of substituted N-glycosyl quinolin-2-ones.
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Table 1. Survey of reaction conditions for the domino Heck/
Buchwald–Hartwig arylation reactions of tetraacetyl-b-gly-
cosylcinnamamide 2a with 4-iodoanisole 1a.[a]
best conditions were found to require: 2a (1 equiv.),
1a (2 equiv.), Pd(OAc)2. (5 mol%), TBAB (3 equiv.),
dioxane in a sealed tube at 1408C for 48 min. Accord-
ingly, 3a was obtained in a an overall 69% yield for
two transformations (entry 1). The palladium catalyst
is necessary to achieve this transformation since no
reaction occurs when the coupling is conducted in the
absence of Pd(OAc)2. Of note, performing the reac-
tion using the 4-bromoanisole instead of the iodinated
derivative 1a furnished the desired product 3a in only
40% yield (entry 12); however, the same reaction
with the 4-chloroanisole failed (entry 13).
Motivated by these results, we next explored the
scope of the coupling reaction of variously b- or a-
substituted N-glycosylcinnamamides with a variety of
aryl halides 1a–m (Scheme 2). Gratifyingly, all the
domino C- and N-arylations proceeded selectively in
good yields. As illustrated in Scheme 2, a variety of
electron-rich and electron-deficient, para- and meta-
substituted aryl iodides effectively undergo reaction
with b-glucopyranosylcinnamamide 2a in yields up to
69% (products 3a–k). In addition, the sterically de-
manding ortho-substitution pattern was tolerated in
the tandem coupling reaction of 1a, furnishing com-
pound 3l in a 64% yield as a mixture of atropoisomers
in a 61:39 ratio (see the Supporting Information).
Interestingly, C-halogen bonds (e.g., Br, Cl, F) were
tolerated in this tandem process affording compounds
3f–h, 3j, 3k and 3m in good yields. The presence of
halogen substituents provided a handle for further
structural diversifications using metal-catalyzed cross-
coupling reactions. Importantly, there is no significant
impact of protecting groups on the reactivity of the
glycosylcinnamamide derivatives since unprotected
carbohydrate 2b reacts similarly as O-acetylated de-
rivatives furnishing the coupling product 3n in a 52%
yield. Of note that in all cases studied, compounds
3a–n were isolated as a single anomer, clearly indicat-
ing that the tandem process is stereoretentive toward
the anomeric configuration.
Entry Base
T
t
TBAB (x
1a
Yield of 3a
[8C] [h] equiv.)
(equiv.) [%][b]
1
2
TBAA 130 24
TBAA 130 48
3
1.5
1.5
1.5
2
2
2
2
2
2
2
45
52
35
56
3
3
3
3
3
3
6
1
3
3
3
3
3
4
5
6
7
8
9
10
11
12
13
TBAA 130 60
TBAA 130 48
TBAA 140 48
KOAc 140 48
NaOAc 140 48
KOAc 140 48
KOAc 140 48
KOAc 140 48
KOAc 140 48
KOAc 140 48
KOAc 140 48
64
69[c]
64
60
[d]
–
56[e]
26[f]
40[g]
0[h]
2
2
2
[a]
Reaction conditions: 1a (1.5 equiv.), 2a (1 equiv.),
Pd(OAc)2 (5 mol%), base (3 equiv.), additive (3 equiv.),
anhydrous dioxane (0.1M). TBAB=(n-Bu)4NBr (tetra-
butylamonium bromide), TBAA=(n-Bu)4NOAc (tetra-
butylamonium acetate).
Yield of isolated 3a.
When 2 equiv. of KOAc were used, 3a was obtained in
only 58% yield.
Yield not determined, only 60% of conversion of 2a.
XantPhos ligand (10 mol%) was added to the reaction.
P(o-tolyl)3 ligand (10 mol%) was added to the reaction.
The reaction of 2a was performed in the presence of 4-
bromoanisole instead of 4-iodoanisole.
[b]
[c]
[d]
[e]
[f]
[g]
In a further set of experiments, we investigated the
scope and generality of the method with respect to
cinnamamidomono- and cinnamamidodisaccharides.
As depicted in Scheme 3, the protocol tolerates differ-
ent glycosylcinnamamides such as b-d-galactoside 2d
and a-d-mannoside 2e to give the corresponding
[h]
The reaction of 2a was performed in the presence of 4-
chloroanisole instead of 4-iodoanisole.
at 1408C is the best combination for the tandem cou- products 3o and 3p in 73% and 69% yields, respec-
pling reactions of 1a (2 equiv.) with 2a. Under these tively. The coupling procedure is not limited only to
conditions, 3a was isolated in a 69% yield as a pure b- mono-glycosylcinnamamides but also works success-
anomer (entry 6). A slightly lower yield was obtained fully with peracetylated b-d-disaccharide 2f derived
when the reaction of 1a and 2a was performed with from d-cellobiose octaacetate. The N-glycosylated
TBAA or NaOAc as bases instead of KOAc (en- quinolin-2-one 3q was obtained in a 72% yield, and
tries 5–7). In a next set of experiments, we attempted the stereochemistry of the 1–4’ glycosidic bond re-
to improve the yield of 3a. After a series of assays in mained intact.
which we added some ligands such as bidentate Xant-
The success of our methodology can be explained
Phos (entry 10) or monodentate tri-o-tolylphosphine through the mechanism suggested in Figure 2. Our hy-
(entry 11) did not lead to any improvement. Thus, the pothesis starts from the Heck coupling cycle[8] which
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Scheme 3. Scope of a- or b-glycosylcinnamamides 2d–f cou-
pling with 4-iodoanisole 1a. Reactions of 2d–f (1 equiv.)
with 1a (2 equiv.) were performed in a flame-dried re-seala-
ble Schlenk tube using Pd(OAc)2 (5 mol%), (n-Bu)4NBr
(3 equiv.), KOAc (3 equiv.) in dioxane (0.1M) at 1408C for
48 h. Yields of isolated products 3 are given.
produces the tri-substituted glycosylcinnamamide in-
termediate (II) in which the geometry of the double
bond was isomerized from E- to Z-configuration. The
reaction begins by oxidative addition of the aryl
iodide to the palladium, which is followed by coordi-
nation and migratory insertion of the olefin to the
À
palladium. An internal C C bond rotation in the s-
alkyl-palladium(II) iodide brings an Csp3-bonded b-
hydrogen in a syn position relative to the palladium
atom. This bond rotation then places the amide in the
À
optimal configuration for the next C N bond cou-
pling. A syn b-hydride elimination gives a hydridopal-
ladium(II) iodide ligated to the arylated alkene. After
a dissociation step, the hydridopalladium(II) halide
undergoes a reversible reductive elimination to regen-
erate the active Pd(0) complex. The base shifts this
equilibrium towards the Pd(0) catalyst by quenching
the hydrogen iodide. Intermediate (II) undergoes
under the same conditions, an oxidative addition in
the Buchwald–Hartwig catalytic cycle[9] through its
carbon-iodine bond to give (III). Then, a coordination
of the nitrogen of the amide to the palladium which is
favorable in the Z-configuration occurs (V), followed
by a base-assisted proton abstraction from the amide
in (VI), and a reductive elimination produces the
final N-glycosylated quinolin-2-one product 3 and re-
generates the catalyst.
Scheme 2. Scope of aryl halides coupling with tetraacetyl b-
glucopyranosylcinnamamides 2a–c. Reactions of 2a–
c (1 equiv.) with 1a–m (2 equiv.) were performed in a flame-
dried re-sealable Schlenk tube using Pd(OAc)2 (5mol%),
(n-Bu)4NBr (3 equiv.), KOAc (3 equiv.) in dioxane (0.1M)
at 1408C for 48h. Yields of isolated products 3 are given.
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Figure 2. Proposed mechanism.
These mechanistic assumptions were supported by 30 h showed that the peak intensity of II decreases
an LC-MS kinetic study of the reaction model at dif- slightly in favour of the formation of the final com-
ferent times. After only 5 h of running the reaction, pound 3a (see the Supporting Information). Interest-
the starting material 2a disappeared completely and ingly, this study allowed us to identify the formation
the intermediate II as well as the final compound 3a of small amounts of two other by-products at reten-
were formed as detected by LC-MS with retention tion times of 14.5 min and 17.4 min, which may corre-
times at 18.3 min and 17.6 min, respectively spond to N-glucosylquinolinone V and the de-iodinat-
(Figure 3). Monitoring the reaction at 16 h, 24 h and ed Heck adduct IV, respectively. These results com-
Figure 3. LC-MS analysis of the reaction of 1a and 2a after 5 h stirring at 1408C
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and purified by flash chromatography over silica gel to
afford the desired product.
bined with data reported in the Supporting Informa-
tion are in agreement with the mechanism suggested
here.
4-(4-Methoxyphenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-
d-glucopyranosyl)-quinolin-2-one (3a): Compound 3a was
prepared according to the general procedure using E-3-(2-
iodophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyr-
anosyl)acrylamide 2a (100 mg, 0.166 mmol) and 4-iodoani-
sole (78 mg, 0.33 mmol). The title compound was obtained
after flash chromatography as a yellow solid; yield: 66 mg
(69%); mp 144–1468C; [a]2D5: +56.0 (c=1.0 in CHCl3);
1H NMR (300 MHz, CDCl3): d=7.99 (d, J=8.2 Hz, 1H),
7.54 (t, J=8.0 Hz, 2H), 7.31 (d, J=8.6 Hz, 2H), 7.18 (dd,
J=7.5, 7.5 Hz, 1H), 6.99 (d, J=8.6 Hz, 2H), 6.91 (d, J=
9.9 Hz, 1H), 6.51 (s, 1H), 5.96 (t, J=9.4 Hz, 1H), 5.46 (t,
J=9.4 Hz, 1H), 5.37 (t, J=9.7 Hz, 1H), 4.34–4.19 (m, 2H),
4.09–4.00 (m, 1H), 3.85 (s, 3H), 2.08 (s, 6H), 1.99 (s, 3H),
1.80 (s, 3H); 13C NMR (75 MHz, CDCl3): d=170.7 (C),
170.0 (C), 169.8 (C), 169.2 (C), 162.4 (C), 160.3 (C), 152.9
(C), 137.9 (C), 130.4 (CH), 130.2 (2CH), 128.9 (C), 128.4
(CH), 123.1 (CH), 121.4 (C), 119.5 (CH), 117.1 (CH), 114.1
(2CH), 80.7 (CH), 75.1 (CH), 74.0 (CH), 68.0 (CH), 67.8
(CH), 61.8 (CH2), 55.4 (CH3), 20.7 (CH3), 20.7 (CH3), 20.6
(CH3), 20.2 (CH3); FT-IR (neat): n=1755, 1647, 1591, 1512,
1371, 1289, 1214, 1114, 1034, 930 cmÀ1; HR-MS (ESI posi-
tive): m/z=604.1795 ([M+Na]+), calcd. for C30H31NO11NaI
(M+Na): 604.1795. Flash chromatography conditions: cyclo-
hexane/EtOAc 100/0 to 50/50; Rf =0.46 (cyclohexane/
EtOAc: 5/5).
Conclusions
In conclusion, we have successfully developed an effi-
cient and practical domino catalytic protocol based on
Pd(0)-catalyzed tandem Heck/Buchwald–Hartwig
coupling of various a- or b-glycosylcinnamamides and
aryl halides. The protocol exhibited a broad substrate
scope with respect to the coupling partners, thus pro-
viding an attractive method to access a large molecu-
lar diversity of 4-aryl-N-glycosylquinolin-2-ones 3 of
biological interest. This protocol developed here is
stereoretentive, functional-group tolerant, and pro-
ceeds in good yields. We believe that this methodolo-
gy will find applications in organic synthetic chemistry
as well as in combinatorial and pharmaceutical scien-
ces.
Experimental Section
General Experimental Methods
4-(4-Methylphenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-
glucopyranosyl)-quinolin-2-one (3b): Compound 3b was pre-
pared according to the general procedure using E-3-(2-iodo-
phenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyrano-
syl)acrylamide 2a (100 mg, 0.166 mmol) and 4-iodotoluene
(72 mg, 0.33 mmol). The title compound was obtained after
flash chromatography as a beige solid; yield: 66 mg (69%);
mp 96–998C; [a]25: +45.5 (c=1.0 in CHCl3); 1H NMR
(300 MHz, CDCl3)D: d=7.98 (d, J=8.7 Hz, 1H), 7.53 (d, J=
7.5 Hz, 1H), 7.51 (d, J=7.8 Hz, 1H), 7.28–7.23 (m, 4H),
7.17 (d, J=7.5 Hz, 1H), 6.92 (d, J=9.8 Hz, 1H), 6.51 (s,
1H), 5.96 (t, J=9.4 Hz, 1H), 5.46 (t, J=9.3 Hz, 1H), 5.37 (t,
J=9.8 Hz, 1H), 4.36–4.12 (m, 2H), 4.10–3.94 (m, 1H), 2.41
(s, 3H), 2.08 (s, 3H), 2.07 (s, 3H), 1.98 (s, 3H), 1.80 (s, 3H);
13C NMR (75 MHz, CDCl3): d=170.6 (C), 167.0 (C), 169.8
(C), 169.2 (C), 162.2 (C), 153.1 (C), 139.1 (C), 138.0 (C),
133.9 (C), 130.4 (CH), 129.4 (2CH), 128.8 (2CH), 128.5
(CH), 123.1 (CH), 121.4 (C), 119.8 (CH), 117.1 (CH), 80.8
(CH), 75.2 (CH), 74.1 (CH), 68.1 (CH), 67.8 (CH), 61.9
(CH2), 21.4 (CH3), 20.8 (CH3), 20.7 (CH3), 20.7 (CH3), 20.3
(CH3); FT-IR (neat): n=1755, 1658, 1595, 1454, 1365, 1206,
The compounds were all identified by usual physical meth-
ods, e.g., 1H NMR, 13C NMR, IR, MS (ESI). 1H and
13C NMR spectra were measured in CDCl3, acetone-d6,
methanol-d4 or DMSO-d6 with
a Bruker Avance-300.
1H NMR chemical shifts are reported in ppm from an inter-
nal standard TMS or of residual solvent peak. 13C NMR
chemical shifts are reported in ppm from the residual sol-
vent peak. IR spectra were measured on a Bruker Vector 22
spectrophotometer. MS were recorded on a Micromass spec-
trometer. Analytical TLC was performed on Merck precoat-
ed silica gel 60F plates. Merck silica gel 60 (0.015–0.040 mm)
was used for column chromatography. Melting points were
recorded on a Bꢄchi B-450 apparatus and are uncorrected.
High resolution mass spectra (HR-MS) were recorded on
a Bruker MicroTOF spectrometer, using ESI with methanol
as the carrier solvent.
General Procedure for the Synthesis of 4-Aryl-N-
glycosylquinolin-2-ones 3a–q
1032, 931 cmÀ1
;
HR-MS (ESI positive): m/z=found
588.1841 ([M+Na]+), calcd. for C30H31NO10NaI (M+Na):
581.1846. Flash chromatography conditions: cyclohexane/
EtOAc 100/0 to 50/50; Rf =0.6 (cyclohexane/EtOAc: 5/5).
4-Phenyl-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyra-
nosyl)-quinolin-2-one (3c): Compound 3c was prepared ac-
cording to the general procedure using (E)-3-(2-iodophen-
yl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyranosyl)ac-
A flame-dried sealed tube was charged with amido sugar
2a–f (0.166 mmol, 1 equiv.), iodoarene 1a–m (0.33 mmol,
2 equiv.), KOAc (0.5 mmol, 3 equiv.), TBAB (0.5 mmol,
3 equiv.), and Pd(OAc)2 (0.008 mmol, 5 mol%). The tube
was capped with a rubber septum, evacuated and backfilled
under argon three times, then dioxane (1.5 mL, 0.1M) was
added through the septum under argon. The septum was re-
placed with a Teflon screw cap. The tube was sealed and the
mixture was stirred at 1408C for 48 h. The resulting suspen-
sion was cooled at room temperature and filtered through
a pad of celite eluting with ethyl acetate and the organic
salts were removed. The filtrate was evaporated to dryness
AHCTUNGTREGrNNUN ylamide 2a (100 mg, 0.17 mmol) and iodobenzene (55 mL,
0.33 mmol). The title compound was obtained after flash
chromatography followed by HPLC as a white solid; yield:
52 mg (56%); mp 118.6–120.48C; [a]2D5: +61.0 (c=1.0 in
1
CHCl3); H NMR (300 MHz, CDCl3): d=8.01 (d, J=8.6 Hz,
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1H), 7.62–7.44 (m, 5H), 7.44–7.32 (m, 2H), 7.19 (dd, J=7.6,
7.6 Hz, 1H), 6.95 (d, J=9.9 Hz, 1H), 6.56 (s, 1H), 5.99 (t,
J=9.4 Hz, 1H), 5.55–5.35 (m, 2H), 4.37–4.21 (m, 2H), 4.13–
4.01 (m, 1H), 2.11 (s, 3H), 2.10 (s, 3H), 2.01 (s, 3H), 1.83 (s,
3H); 13C NMR (75 MHz, CDCl3): d=170.6 (C), 170.0 (C),
169.8 (C), 169.2 (C), 162.2 (C), 153.0 (C), 138.0 (C), 136.8
(C), 130.5 (CH), 129.1 (CH), 128.9 (2CH), 128.7 (2CH),
128.4 (CH), 123.1 (CH), 121.2 (C), 120.0 (CH), 117.1 (CH),
80.7 (CH), 75.2 (CH), 74.0 (CH), 68.0 (CH), 67.8 (CH), 61.8
(CH2), 20.8 (CH3), 20.7 (CH3), 20.7 (CH3), 20.3 (CH3); FT-
IR (neat): n=1755, 1738, 1659, 1490, 1378, 1206, 1032, 752,
3H); 13C NMR (75 MHz, CDCl3): d=170.61 (C), 169.99 (C),
169.79 (C), 169.26 (C), 162.16 (C), 153.06 (C), 137.97 (C),
134.18 (C), 133.33 (C), 133.13 (C), 130.54 (CH), 128.53
(CH), 128.36 (2CH), 128.25 (CH), 127.91 (CH), 127.05
(CH), 126.93 (CH), 126.46 (CH), 123.18 (CH), 121.30 (CH),
120.25 (C), 117.09 (CH), 80.72 (CH), 75.12 (CH), 73.99
(CH), 68.00 (CH), 67.78 (CH), 61.82 (CH2), 20.85 (CH3),
20.75 (CH3), 20.73 (CH3), 20.36 (CH3); FT-IR (neat): n=
1756, 1657, 1596, 1365, 1206, 1032, 907, 823, 757 cmÀ1; HR-
MS (ESI): m/z=602.2039, calcd. for C33H32NO10 [M+H]+:
602.2026, m/z=624.1847, calcd. found C33H31NO10Na [M+
Na]+: 624.1846. Flash chromatography conditions: column
25 g, flow rate 18 mLminÀ1, cyclohexane/EtOAc 100/0 to 50/
50; Rf =0.29 cyclohexane/EtOAc 60/40; HPLC conditions:
Xbridge column C18 4.6ꢅ150 mm 5 mm, H2O+0.1%TFA/
ACN 50/50 to 0/100 in 15 min, tR =9.1 min.
703 cmÀ1
;
HR-MS (ESI): m/z=552.1867, calcd. for
C29H30NO10 [M+H]+: 552.1870, m/z=574.1699, calcd. for
C29H29NO10Na [M+Na]+: 574.1689. Flash chromatography
conditions: column 25 g, flow rate 18 mLminÀ1, cyclohex-
ane/EtOAc 100/0 to 50/50. Rf =0.30 cyclohexane/EtOAc 60/
40. HPLC conditions: Xbridge column C18 4.6ꢅ150 mm
5 mm, H2O/MeOH 40/60 to 0/100 in 15 min, tR =8.1 min.
4-(4-Isopropylphenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-
d-glucopyranosyl)-quinolin-2-one (3d): Compound 3d was
prepared according to the general procedure using (E)-3-(2-
iodophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyr-
anosyl)acrylamide 2a (100 mg, 0.17 mmol) and 1-iodo-4-iso-
propylbenzene (55 mL, 0.33 mmol). The title compound was
obtained after flash chromatography followed by HPLC as
a white solid; yield: 59 mg (60%); mp 162.9–164.58C; [a]2D5:
4-(4-Fluorophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-
glucopyranosyl)-quinolin-2-one (3f): Compound 3f was pre-
pared according to the general procedure using (E)-3-(2-io-
dophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyra-
nosyl)acrylamide 2a (100 mg, 0.17 mmol) and 1-fluoro-4-io-
dobenzene (38 mL, 0.33 mmol). The title compound was ob-
tained after flash chromatography followed by HPLC as
a white solid; yield: 49 mg (52%); mp 106.4–108.28C; [a]2D5:
1
+51.4 (c=1.0 in CHCl3); H NMR (300 MHz, CDCl3): d=
8.01 (d, J=8.6 Hz, 1H), 7.60–7.51 (m, 1H), 7.45 (dd, J=8.1,
1.4 Hz, 1H), 7.42–7.32 (m, 2H), 7.25–7.15 (m, 3H), 6.93 (d,
J=9.9 Hz, 1H), 6.53 (s, 1H), 5.98 (t, J=9.4 Hz, 1H), 5.54–
5.35 (m, 2H), 4.36–4.19 (m, 2H), 4.10–4.01 (m, 1H), 2.10 (s,
3H), 2.09 (s, 3H), 2.00 (s, 3H), 1.83 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=170.6 (C), 169.9 (C), 169.8 (C), 169.2
(C), 163.2 (d, JC,F =249.0 Hz, C), 162.0 (C), 152.0 (C), 138.0
(C), 132.7 (d, JC,F =3.1 Hz, C), 130.7 (d, JC,F =8.4 Hz, 2CH),
130.6 (CH), 128.1 (CH), 123.2 (CH), 121.1 (C), 120.2 (CH),
117.1 (CH), 115.9 (d, JC,F =21.8 Hz, 2CH), 80.7 (CH), 75.1
(CH), 74.0 (CH), 68.0 (CH), 67.8 (CH), 61.8 (CH2), 20.8
(CH3), 20.7 (CH3), 20.7 (CH3), 20.3 (CH3); FT-IR (neat): n=
1755, 1659, 1598, 1366, 1206, 1032, 844, 756 cmÀ1; HR-MS
(ESI): m/z=570.1790, calcd. for C29H29NO10F [M+H]+:
570.1775, m/z=592.1607, calcd. for C29H28NO10FNa [M+
Na]+: 592.1595. Flash chromatography conditions: column
25 g, flow rate 18 mLminÀ1, cyclohexane/EtOAc 100/0 to 50/
50; Rf =0.34 cyclohexane/EtOAc 60/40; HPLC conditions:
Xbridge column C18 4.6ꢅ150 mm 5 mm, H2O/MeOH 40/60
to 0/100 in 15 min, tR =8.2 min.
1
(c 1.0 in CHCl3); H NMR (300 MHz, CDCl3): d=8.01 (d,
J=8.5 Hz, 1H), 7.57 (d, J=7.8 Hz, 1H), 7.54 (d, J=9.3 Hz,
1H), 7.38–7.25 (m, 4H), 7.19 (dd, J=7.6, 7.6 Hz, 1H), 6.94
(d, J=9.9 Hz, 1H), 6.55 (s, 1H), 5.99 (t, J=9.3 Hz, 1H),
5.52–5.36 (m, 2H), 4.36–4.21 (m, 2H), 4.06 (d, J=9.7 Hz,
1H), 2.98 (dq, J=13.8, 6.9 Hz, 1H), 2.10 (s, 3H), 2.10 (s,
3H), 2.01 (s, 3H), 1.83 (s, 3H), 1.32 (s, 3H), 1.29 (s, 3H);
13C NMR (75 MHz, CDCl3): d=170.6 (C), 170.0 (C), 169.8
(C), 169.2 (C), 162.2 (C), 153.1 (C), 150.0 (C), 137.9 (C),
134.1 (C), 130.4 (CH), 128.9 (2CH), 128.5 (CH), 126.8
(2CH), 123.1 (CH), 121.3 (C), 119.8 (CH), 117.0 (CH), 80.7
(CH), 75.1 (CH), 74.0 (CH), 68.0 (CH), 67.7 (CH), 61.8
(CH2), 34.1 (CH), 24.0 (2*CH3), 20.8 (CH3), 20.7 (CH3), 20.7
(CH3), 20.3 (CH3); FT-IR (neat): n=1756, 1658, 1595, 1365,
1206, 1032, 839, 756 cmÀ1; HR-MS (ESI): m/z=594.2337,
calcd. for C32H36NO10 [M+H]+: 594.2339, m/z=616.2155,
calcd. for C32H35NO10Na [M+Na]+: 616.2159. Flash chroma-
tography conditions: column 25 g, flow rate 18 mLminÀ1, cy-
clohexane/EtOAc 100/0 to 50/50; Rf =0.32 cyclohexane/
EtOAc 60/40; HPLC conditions: Xbridge column C18 4.6ꢅ
150 mm 5 mm, H2O+0.1%TFA/ACN 50/50 to 0/100 in
15 min, tR =10.8 min.
4-(4-Bromophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-
glucopyranosyl)-quinolin-2-one (3g): Compound 3g was pre-
pared according to the general procedure using (E)-3-(2-io-
dophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyra-
nosyl)acrylamide 2a (100 mg, 0.17 mmol) and 1-bromo-4-io-
dobenzene (94 mg, 0.33 mmol). The title compound was ob-
tained after flash chromatography followed by HPLC as
a white solid; yield: 52 mg (50%); mp 108.2–110.18C; [a]2D5:
4-(2-Naphthyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glu-
copyranosyl)-quinolin-2-one (3e): Compound 3e was pre-
pared according to the general procedure using (E)-3-(2-io-
dophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyra-
nosyl)acrylamide 2a (100 mg, 0.17 mmol) and 2-iodonaph-
thalene (84 mg, 0.33 mmol). The title compound was ob-
tained after flash chromatography followed by HPLC as
a white solid; yield: 63 mg (63%); mp 132.7–134.18C; [a]2D5:
1
+44.0 (c=1.0 in CHCl3); H NMR (300 MHz, CDCl3): d=
8.04 (d, J=8.5 Hz, 1H), 7.65 (d, J=8.3 Hz, 2H), 7.62–7.56
(m, 1H), 7.47 (d, J=7.5 Hz, 1H), 7.29 (d, J=6.7 Hz, 2H),
7.25–7.19 (m, 1H), 6.95 (d, J=9.9 Hz, 1H, Hb), 6.55 (s, 1H),
6.00 (t, J=9.3 Hz, 1H), 5.56–5.36 (m, 2H), 4.35–4.25 (m,
2H), 4.11–4.05 (m, 1H), 2.13 (s, 6H), 2.04 (s, 3H), 1.86 (s,
3H); 13C NMR (75 MHz, CDCl3: d=170.6 (C), 170.0 (C),
169.8 (C), 169.3 (C), 162.0 (C), 151.9 (C), 138.0 (C), 135.7
(C), 132.1 (2CH), 130.8 (CH), 130.6 (2CH), 128.1 (CH),
1
+70.6 (c=1.0 in CHCl3); H NMR (300 MHz, CDCl3): d=
8.05 (d, J=8.6 Hz, 1H), 7.99–7.85 (m, 4H), 7.63–7.52 (m,
4H), 7.49 (dd, J=8.4, 1.5 Hz, 1H), 7.19 (dd, J=7.5, 7.5 Hz,
1H), 6.98 (d, J=10.0 Hz, 1H), 6.66 (s, 1H), 6.03 (t, J=
9.4 Hz, 1H), 5.57–5.36 (m, 2H), 4.38–4.23 (m, 2H), 4.14–
4.04 (m, 1H), 2.12 (s, 3H), 2.11 (s, 3H), 2.03 (s, 3H), 1.87 (s,
Adv. Synth. Catal. 0000, 000, 0 – 0
7
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123.5 (C), 123.3 (CH), 120.9 (C), 120.1 (CH), 117.2 (CH),
80.8 (CH), 75.2 (CH), 74.0 (CH), 68.0 (CH), 67.8 (CH), 61.8
(CH2), 20.9 (CH3), 20.7 (2CH3), 20.3 (CH3); FT-IR (neat):
n=1755, 1739, 1658, 1486, 1454, 1365, 1206, 1031, 930, 907,
832, 756 cmÀ1; HR-MS (ESI): m/z=630.0983, calcd. for
C29H29NO10Br [M+H]+: 630.0975, m/z=652.0786, calcd. for
C29H28NO10BrNa [M+Na]+: 652.0794. Flash chromatogra-
phy conditions: column 25 g, flow rate 18 mLminÀ1, cyclo-
hexane/EtOAc 100/0 to 50/50; Rf =0.55 cyclohexane/EtOAc
60/40; HPLC conditions: Xselect column C18 4.6ꢅ150 mm
5 mm, H2O/MeOH 40/60 to 0/100 in 15 min, tR =10.0 min.
4-(4-Chlorophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-
glucopyranosyl)-quinolin-2-one (3h): Compound 3h was pre-
pared according to the general procedure using (E)-3-(2-io-
dophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyra-
nosyl)acrylamide 2a (100 mg, 0.17 mmol) and 1-chloro-4-io-
dobenzene (79 mg, 0.33 mmol). The title compound was ob-
tained after flash chromatography followed by HPLC as
a white solid; yield: 56 mg (58%); mp 113.7–115.68C; [a]2D5:
604.1800, calcd. for C30H31NO11Na [M+Na]+: 604.1795.
Flash chromatography conditions: column 25 g, flow rate
18 mLminÀ1, cyclohexane/EtOAc 100/0 to 50/50; Rf =0.45
cyclohexane/EtOAc 50/50; HPLC conditions: Xbridge
column C18 4.6ꢅ150 mm 5 mm, H2O+0.1% AF/ACN 90/10
to 0/100 in 15 min, tR =12.3 min.
4-(3-Bromophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-
glucopyranosyl)-quinolin-2-one (3j): Compound 3j was pre-
pared according to the general procedure using (E)-3-(2-io-
dophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyra-
nosyl)acrylamide 2a (100 mg, 0.17 mmol) and 1-bromo-3-io-
dobenzene (43 mL, 0.33 mmol). The title compound was ob-
tained after flash chromatography followed by HPLC as
a white solid; yield: 58 mg (55%); mp 108.7–110.58C; [a]2D5:
1
+54.8 (c=1.0 in CHCl3); H NMR (300 MHz, CDCl3): d=
8.02 (d, J=8.6 Hz, 1H), 7.62 (d, J=8.1 Hz, 1H), 7.59 (d, J=
8.3 Hz, 1H), 7.54 (s, 1H), 7.44 (d, J=8.0 Hz, 1H), 7.37–7.30
(m, 2H), 7.24–7.18 (m, 1H), 6.93 (d, J=9.9 Hz, 1H), 6.53 (s,
1H), 5.98 (t, J=9.4 Hz, 1H), 5.20–5.36 (m, 2H), 4.34–4.22
(m, 2H), 4.10–4.03 (m, 1H), 2.11 (s, 3H), 2.10 (s, 3H), 2.01
(s, 3H), 1.84 (s, 3H); 13C NMR (75 MHz, CDCl3): d=170.6
(C), 170.0 (C), 169.8 (C), 169.2 (C), 161.9 (C), 151.4 (C),
138.8 (C), 138.0 (C), 132.2 (CH), 131.8 (CH), 130.8 (CH),
130.4 (CH), 128.1 (CH), 127.6 (CH), 123.4 (CH), 122.6 (C),
120.8 (C), 120.3 (CH), 117.2 (CH), 80.8 (CH), 75.2 (CH),
74.0 (CH), 68.1 (CH), 67.8 (CH), 61.9 (CH2), 20.9 (CH3),
20.8 (CH3), 20.7 (CH3), 20.4 (CH3); FT-IR (neat): n=1756,
1660, 1599, 1366, 1206, 1032, 908, 756, 703 cmÀ1; HR-MS
(ESI): m/z=630.0975, calcd. for C29H29NO10Br [M+H]+:
630.0975, m/z=652.0767, calcd. for C29H28NO10BrNa [M+
Na]+: 652.0794. Flash chromatography conditions: column
25 g, flow rate 18 mLminÀ1, cyclohexane/EtOAc 100/0 to 50/
50; Rf =0.30 cyclohexane/EtOAc 60/40; HPLC conditions:
Xselect column C18 4.6ꢅ150 mm 5 mm, H2O/MeOH 40/60 to
0/100 in 15 min, tR =9.8 min.
1
+51.0 (c=1.0 in CHCl3); H NMR (300 MHz, CDCl3): d=
8.02 (d, J=8.5 Hz, 1H), 7.63–7.53 (m, 1H), 7.51–7.41 (m,
3H), 7.33 (d, J=8.3 Hz, 2H), 7.23–7.16 (m, 1H), 6.93 (d, J=
9.6 Hz, 1H), 6.53 (s, 1H), 5.98 (t, J=9.2 Hz, 1H), 5.56–5.32
(m, 2H), 4.35–4.22 (m, 2H), 4.10–4.01 (m, 1H), 2.11 (s, 6H),
2.01 (s, 3H), 1.84 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
170.6 (C), 170.0 (C), 169.8 (C), 169.2 (C), 162.0 (C), 151.9
(C), 138.0 (C), 135.4 (C), 135.2 (C), 130.7 (CH), 130.3
(2CH), 129.1 (2CH), 128.1 (CH), 123.3 (CH), 120.9 (C),
120.1 (CH), 117.2 (CH), 80.8 (CH), 75.2 (CH), 74.0 (CH),
68.0 (CH), 67.9 (CH), 61.8 (CH2), 20.9 (CH3), 20.8 (CH3),
20.7 (CH3), 20.3 (CH3); FT-IR (neat): n=1755, 1659, 1599,
1366, 1206, 1032, 836, 755 cmÀ1; HR-MS (ESI): m/z=
586.1483, calcd. for C29H29NO10Cl [M+H]+: 586.1480, m/z=
608.1311, calcd. for C29H28NO10ClNa [M+Na]+: 608.1299.
Flash chromatography conditions: column 25 g, flow rate
18 mLminÀ1, cyclohexane/EtOAc 100/0 to 50/50; Rf =0.29
cyclohexane/EtOAc 60/40; HPLC conditions: Xbridge
column C18 4.6ꢅ150 mm 5 mm, H2O+0.1% TFA/ACN 50/50
to 20/80 in 20 min, tR =10.8 min.
4-(3-Chlorophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-
glucopyranosyl)-quinolin-2-one (3k): Compound 3k was pre-
pared according to the general procedure using (E)-3-(2-io-
dophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyra-
nosyl)acrylamide 2a (100 mg, 0.17 mmol) and 1-chloro-3-io-
dobenzene (42 mL, 0.33 mmol). The title compound was ob-
tained after flash chromatography followed by HPLC as
a white solid; yield: 60 mg (62%); mp 135.5–137.38C; [a]2D5:
4-(3-Methoxyphenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-
d-glucopyranosyl)-quinolin-2-one (3i): Compound 3i was
prepared according to the general procedure using (E)-3-(2-
iodophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyr-
anosyl)acrylamide 2a (100 mg, 0.17 mmol) and 1-iodo-3-me-
thoxybenzene (40 mL, 0.33 mmol). The title compound was
obtained after flash chromatography followed by HPLC as
a white solid; yield: 64 mg (66%); mp 105.3–107.28C; [a]2D5:
1
+32.4 (c=1.0 in CHCl3); H NMR (300 MHz, CDCl3): d=
8.04 (d, J=8.6 Hz, 1H), 7.60 (dd, J=7.9, 7.9 Hz, 1H), 7.52–
7.38 (m, 4H), 7.34–7.20 (m, 2H), 6.95 (d, J=10.0 Hz, 1H),
6.57 (s, 1H), 6.00 (t, J=9.5 Hz, 1H5.54–5.38 (m, 2H), 4.40–
4.23 (m, 2H), 4.13–4.03 (m, 1H), 2.13 (s, 6H), 2.04 (s, 3H),
1.87 (s, 3H); 13C NMR (75 MHz, CDCl3): d=170.6 (C),
170.0 (C), 169.8 (C), 169.2 (C), 162.0 (C), 151.6 (C), 138.5
(C), 138.0 (C), 134.8 (C), 130.8 (CH), 130.1 (CH), 129.3
(CH), 128.9 (CH), 128.1 (CH), 127.1 (CH), 123.4 (CH),
120.8 (C), 120.2 (CH), 117.2 (CH), 80.8 (CH), 75.2 (CH),
74.0 (CH), 68.0 (CH), 67.8 (CH), 61.8 (CH2), 20.9 (CH3),
20.8 (CH3), 20.7 (CH3), 20.3 (CH3); FT-IR (neat): n=1754,
1659, 1598, 1367, 1207, 1033, 871, 753 cmÀ1; HR-MS (ESI):
m/z=586.1479, calcd. for C29H29NO10Cl [M+H]+: 586.1480,
m/z=608.1304, calcd. for C29H28NO10ClNa [M+Na]+:
608.1299. Flash chromatography conditions: column 25 g,
flow rate 18 mLminÀ1, cyclohexane/EtOAc 100/0 to 50/50;
Rf =0.30 cyclohexane/EtOAc 60/40; HPLC conditions:
1
+60.5 (c=1.0 in CHCl3); H NMR (300 MHz, CDCl3): d=
8.00 (d, J=8.5 Hz, 1H), 7.56 (dd, J=7.1, 1.7 Hz, 1H), 7.53
(d, J=7.6 Hz, 1H), 7.43–7.35 (m, 1H), 7.23–7.15 (m, 1H),
7.03–6.88 (m, 4H), 6.55 (s, 1H), 6.01 (t, J=9.4 Hz, 1H),
5.52–5.36 (m, 2H), 4.35–4.20 (m, 2H), 4.14–4.00 (m, 1H),
3.83 (s, 3H), 2.10 (s, 3H), 2.09 (s, 3H), 2.01 (s, 3H), 1.83 (s,
3H); 13C NMR (75 MHz, CDCl3): d=170.6 (C), 170.0 (C),
169.8 (C), 169.2 (C), 162.1 (C), 159.7 (C), 152.9 (C), 138.0
(C), 137.9 (C), 130.5 (CH), 129.8 (CH), 128.4 (CH), 123.1
(CH), 121.2 (CH), 121.1 (C), 119.8 (CH), 117.0 (CH), 114.5
(CH), 114.5 (CH), 80.6 (CH), 75.1 (CH), 74.0 (CH), 68.0
(CH), 67.7 (CH), 61.8 (CH2), 55.5 (CH3), 20.8 (CH3), 20.7
(CH3), 20.7 (CH3), 20.3 (CH3); FT-IR (neat): n=1755, 1658,
1596, 1366, 1206, 1031, 909, 756 cmÀ1; HR-MS (ESI): m/z=
582.1997 calcd. for C30H32NO11 [M+H]+: 582.1975, m/z=
Adv. Synth. Catal. 0000, 000, 0 – 0
8
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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FULL PAPERS
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Xbridge column C18 4.6ꢅ150 mm 5 mm, H2O/MeOH 40/60
to 0/100 in 15 min, tR =9.8 min.
(C), 161.9 (C), 160.7 (C), 151.8 (C), 137.0 (C), 133.2 (CH),
130.7 (CH), 130.3 (2CH), 128.3 (C), 123.2 (C), 120.7 (CH),
118.7 (CH), 116.4 (C), 114.5 (2CH), 80.8 (CH), 75.3 (CH),
73.9 (CH), 68.0 (CH), 67.8 (CH), 61.8 (CH2), 55.6 (CH3),
20.8 (CH3), 20.7 (2CH3), 20.3 (CH3); FT-IR (neat): n=1756,
1659, 1425, 1207, 1030, 840 cmÀ1; HR-MS (ESI): m/z=
660.1075, calcd. for C30H31NO11Br [M+H]+: 660.1080, m/z=
682.0896, calcd. for C30H30NO11BrNa [M+Na]+: 682.0900.
Flash chromatography conditions: column 25 g, flow rate
18 mLminÀ1, cyclohexane/EtOAc 100/0 to 50/50; Rf =0.20
cyclohexane/EtOAc 60/40; HPLC conditions: Xselect
column C18 4.6ꢅ150 mm 5 mm, H2O/MeOH 40/60 to 0/100 in
15 min, tR =10.6 min.
4-(1-Naphthyl-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glu-
copyranosyl)-quinolin-2-one (3l): Compound 3l was pre-
pared according to the general procedure using (E)-3-(2-io-
dophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-glucopyra-
nosyl)acrylamide 2a (100 mg, 0.17 mmol) and 1-iodonaph-
thalene (84 mg, 0.33 mmol). The title compound was ob-
tained after flash chromatography followed by HPLC as
a white solid; yield: 64 mg (61/39 ratio of the two atro-
poisomers, 64%); mp 154.6–156.38C; [a]2D5: +48.8 (c=1.0 in
1
CHCl3); H NMR (300 MHz, CDCl3): d(major atropoisom-
er)=8.13–8.01 (m, 1H), 7.97 (d, J=8.3 Hz, 1H), 7.93 (d, J=
8.1 Hz, 1H), 7.60–7.34 (m, 6H), 7.09–6.94 (m, 3H), 6.67 (d,
J=2.6 Hz, 1H), 6.08–5.95 (m, 1H), 5.59–5.38 (m, 2H), 4.40–
4.26 (m, 2H), 4.15–4.07 (m, 1H), 2.14 (s, 3H), 2.12 (s, 3H),
2.04 (s, 3H), 1.91 (s, 3H); d(minor atropoisomer)=8.13–8.01
(m, 1H), 7.97 (d, J=8.3 Hz, 1H), 7.93 (d, J=8.1 Hz, 1H),
7.60–7.34 (m, 6H), 7.09–6.94 (m, 3H), 6.67 (d, J=2.6 Hz,
1H), 6.08–5.95 (m, 1H), 5.59–5.38 (m, 2H), 4.40–4.26 (m,
2H), 4.15–4.07 (m, 1H), 2.14 (s, 3H), 2.12 (s, 3H), 2.04 (s,
3H), 1.91 (s, 3H); 13C NMR (75 MHz, CDCl3) d(major atro-
poisomer)=170.66 (C), 170.00 (C), 169.83 (C), 169.17 (C),
162.35 (C), 152.26 (C), 137.73 (C), 134.32 (C), 133.48 (C),
131.43 (C), 130.63 (CH), 129.39 (CH), 128.83 (CH), 128.52
(CH), 126.81 (CH), 126.66 (CH), 126.41 (CH), 125.65 (CH),
125.55 (CH), 123.35 (CH), 122.36 (C), 121.33 (CH), 117.00
(CH), 81.17 (CH), 75.15 (CH), 73.81 (CH), 68.12 (CH),
68.02 (CH), 61.85 (CH2), 20.89 (CH3), 20.77 (2CH3), 20.37
(CH3); d(minor atropoisomer)=170.66 (C), 170.00 (C),
169.83 (C), 169.27 (C), 162.21 (C), 152.48 (C), 137.62 (C),
134.40 (C), 133.48 (C), 131.43 (C), 130.63 (CH), 129.33
(CH), 128.90 (CH), 128.52 (CH), 126.81 (CH), 126.76 (CH),
126.48 (CH), 125.82 (CH), 125.35 (CH), 123.25 (CH), 122.16
(C), 121.33 (CH), 116.89 (CH), 80.83 (CH), 75.25 (CH),
74.03 (CH), 68.02 (CH), 67.90 (CH), 61.85 (CH2), 20.89
(CH3), 20.77 (2CH3), 20.37 (CH3); FT-IR (neat): n=1756,
1659, 1598, 1366, 1208, 1032, 781, 756 cmÀ1; HR-MS (ESI):
m/z=602.2024, calcd. for C33H32NO10 [M+H]+: 602.2026,
m/z=624.1849, calcd. for C33H31NO10Na [M+Na]+:
624.1846. Flash chromatography conditions: column 25 g,
flow rate 18 mLminÀ1, cyclohexane/EtOAc 100/0 to 50/50;
Rf =0.31 cyclohexane/EtOAc 60/40; HPLC conditions:
Xbridge column C18 4.6ꢅ150 mm 5 mm, H2O+0.1%AF/
ACN 60/40 to 20/80 in 20 min, tR =14.8 min; LC-MS (TOF):
39/61 ratio of the two atropoisomers.
4-(4-Methoxyphenyl)-N-(1-deoxy-b-d-glucopyranosyl)-
quinolin-2-one (3n): Compound 3n was prepared according
to the general procedure using (E)-3-(2-iodophenyl)-N-(1-
deoxy-b-d-glucopyranosyl)acrylamide 2b (60 mg, 0.14 mmol)
and 1-iodo-4-methoxybenzene (65 mg, 0.28 mmol). The title
compound was obtained after flash chromatography as
a white solid; yield: 32 mg (52%); mp 186.7–188.68C; [a]2D5:
1
+15.5 (c=1.0 in MeOH); H NMR (300 MHz, MeOH): d=
8.22 (d, J=8.7 Hz, 2H), 7.25 (dd, J=7.4, 7.4 Hz, 1H), 7.11
(d, J=8.7 Hz, 2H), 6.62 (d, J=9.8 Hz, 1H), 6.55 (s, 1H),
4.40–4.31 (m, 1H), 4.00–3.83 (m, 2H), 3.90 (s, 3H), 3.68–
3.58 (m, 3H); 13C NMR (75 MHz, nethanol-d4): d=164.9
(C), 161.9 (C), 154.3 (C), 139.4 (C), 131.3 (3CH), 130.2 (C),
128.9 (CH), 124.0 (CH), 122.9 (C), 120.5 (CH), 119.6 (CH),
115.2 (2CH), 85.0 (CH), 81.8 (CH), 79.7 (CH), 71.3 (CH),
70.6 (CH), 62.6 (CH2), 55.9 (CH3); FT-IR (neat): n=3383,
1641, 1574, 1244, 1070, 1029, 885, 836, 754 cmÀ1; HR-MS
(ESI): m/z=414.1549, calcd. for C22H24NO7 [M+H]+:
41401553, m/z=436.1378, calcd. for C22H23NO7Na [M+
Na]+: 436.1372. Flash chromatography conditions: column
12 g, flow rate 10 mLminÀ1, cyclohexane/EtOAc 100/0 to 0/
100 then DCM/MeOH 100/0 to 90/10; Rf =0.37 DCM/
MeOH 90/10.
4-(4-Methoxyphenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-
d-galactopyranosyl)-quinolin-2-one (3o): Compound 3o was
prepared according to the general procedure using (E)-3-(2-
iodophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-b-d-galacto-
pyranosyl)acrylamide 2d (100 mg, 0.17 mmol) and 1-iodo-4-
methoxybenzene (78 mg, 0.33 mmol). The title compound
was obtained after flash chromatography as a white solid;
yield: 70 mg (73%); mp 98.8–100.78C; [a]2D5: +19.6 (c=1.0
in CHCl3); 1H NMR (300 MHz, CDCl3): d=8.26 (d, J=
8.6 Hz, 1H), 7.59 (d, J=7.3 Hz, 1H), 7.52 (dd, J=7.8,
7.8 Hz, 1H), 7.36 (d, J=8.6 Hz, 2H), 7.19 (dd, J=7.6,
7.6 Hz, 1H), 7.01 (d, J=8.6 Hz, 2H), 6.91 (d, J=9.7 Hz,
1H), 6.54 (s, 1H), 6.13 (t, J=9.8 Hz, 1H), 5.62 (d, J=
3.0 Hz, 1H), 5.31 (dd, J=9.8, 3.1 Hz, 1H), 4.33–4.23 (m,
2H), 4.18–4.12 (m, 1H), 3.88 (s, 3H), 2.33 (s, 3H), 2.06 (s,
3H), 2.01 (s, 3H), 1.87 (s, 3H); 13C NMR (75 MHz, CDCl3):
d=170.5 (C), 170.0 (C), 169.7 (C), 169.4 (C), 162.2 (C),
160.3 (C), 152.7 (C), 138.2 (C), 130.3 (2CH), 130.1 (CH),
129.0 (C), 128.3 (CH), 122.8 (CH), 121.3 (C), 119.6 (CH),
117.1 (CH), 114.1 (2CH), 80.7 (CH), 73.6 (CH), 72.0 (CH),
67.6 (CH), 65.6 (CH), 61.6 (CH2), 55.5 (CH3), 20.9 (CH3),
20.8 (CH3), 20.7 (CH3), 20.4 (CH3); FT-IR (neat): n=1750,
1653, 1368, 1208, 1053, 837, 757 cmÀ1; HR-MS (ESI): m/z=
582.1992, calcd. for C30H32NO11 [M+H]+: 582.1975, m/z=
604.1787, calcd. for C30H31NO11Na [M+Na]+: 604.1795.
Flash chromatography conditions: column 25 g, flow rate
7-Bromo-4-(4-Methoxyphenyl)-N-(2,3,4,6-tetra-O-acetyl-
1-deoxy-b-d-glucopyranosyl)-quinolin-2-one (3m): Com-
pound 3m was prepared according to the general procedure
using
acetyl-1-deoxy-b-d-glucopyranosyl)acrylamide 2c (114 mg,
0.17 mmol) and 1-iodo-4-methoxybenzene (78 mg,
(E)-3-(5-bromo-2-iodophenyl)-N-(2,3,4,6-tetra-O-
0.33 mmol). The title compound was obtained after flash
chromatography followed by HPLC as a white solid; yield:
66 mg (58%); mp 106.4–108.08C; [a]2D5: À6.6 (c=1.0 in
1
CHCl3); H NMR (300 MHz, CDCl3): d=7.89 (d, J=9.3 Hz,
1H), 7.72–7.56 (m, 2H), 7.32 (d, J=8.6 Hz, 2H), 7.03 (d, J=
8.6 Hz, 2H), 6.89 (d, J=10.0 Hz, 1H), 6.55 (s, 1H), 5.90 (t,
J=9.5 Hz, 1H), 5.56–5.42 (m, 1H), 5.42–5.28 (m, 1H), 4.37–
4.19 (m, 2H), 4.05 (d, J=9.6 Hz, 1H), 3.89 (s, 3H), 2.11 (s,
3H), 2.10 (s, 3H), 2.02 (s, 3H), 1.84 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=170.6 (C), 170.0 (C), 169.8 (C), 169.3
Adv. Synth. Catal. 0000, 000, 0 – 0
9
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18 mLminÀ1, cyclohexane/EtOAc 100/0 to 50/50; Rf =0.44
cyclohexane/EtOAc 50/50.
Acknowledgements
4-(4-Methoxyphenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-a-
d-mannopyranosyl)-quinolin-2-one (3p): Compound 3p was
prepared according to the general procedure using (E)-3-(2-
iodophenyl)-N-(2,3,4,6-tetra-O-acetyl-1-deoxy-a-d-manno-
pyranosyl)acrylamide 2e (100 mg, 0.17 mmol) and 1-iodo-4-
methoxybenzene (78 mg, 0.33 mmol). The title compound
was obtained after flash chromatography as a white solid;
yield: 36 mg (47%); mp 146.3–148.18C; [a]2D5: À52.3 (c=1.0
in CHCl3); 1H NMR (300 MHz, CDCl3): d=8.46 (d, J=
8.8 Hz, 1H), 7.51 (dd, J=8.1, 1.3 Hz, 1H), 7.43 (dd, J=8.8,
7.1 Hz, 1H), 7.33 (d, J=8.7 Hz, 2H), 7.12 (dd, J=7.6,
7.6 Hz, 1H), 7.00 (d, J=8.7 Hz, 2H), 6.88 (br. s, 1H), 6.56
(s, 1H), 5.77 (d, J=3.8 Hz, 1H), 5.56–5.43 (m, 2H), 4.35–
4.25 (m, 2H), 4.01–3.95 (m, 1H), 3.87 (s, 3H), 2.13 (s, 3H),
2.10 (s, 3H), 1.99 (s, 3H), 1.79 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=170.6 (C), 170.0 (C), 169.6 (C), 169.6 (C), 161.8
(C), 160.2 (C), 152.4 (C), 138.7 (C), 130.3 (2CH), 129.2 (C),
129.0 (CH), 127.6 (CH), 122.5 (CH), 121.5 (C), 120.2 (CH),
119.6 (CH), 114.1 (2CH), 82.7 (CH), 76.3 (CH), 70.9 (CH),
69.9 (CH), 65.8 (CH), 62.3 (CH2), 55.5 (CH3), 21.0 (CH3),
20.9 (CH3), 20.8 (CH3), 20.6 (CH3); FT-IR (neat): n=1746,
1658, 1367, 1245, 1222, 1102, 1055, 837, 761 cmÀ1; HR-MS
(ESI): m/z=582.1963, calcd. for C30H32NO11 [M+H]+:
582.1975, m/z=604.1778, calcd. for C30H31NO11Na [M+
Na]+: 604.1795. Flash chromatography conditions: column
25 g, flow rate 18 mLminÀ1, cyclohexane/EtOAc 100/0 to 60/
40; Rf =0.46 cyclohexane/EtOAc 60/40.
Authors acknowledge support of this project by CNRS, Uni-
versity Paris Sud, ANR (ANR-15-CE29-0002) and by la
Ligue Contre le Cancer through an Equipe Labellisꢀe 2014
grant. We also thank ARC (association pour la recherche sur
le cancer) for their financial support of this research and for
a Ph.D. grant to T. T. H. Luong. Our laboratory is a member
of the Laboratory of Excellence LERMIT supported by
a grant (ANR-10-LABX-33).
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C42H48NO19 [M+H]+: 870.2821, m/z=892.2659, calcd. for
C42H47NO19Na [M+Na]+: 892.2640. Flash chromatography
conditions: column 25 g, flow rate 18 mLminÀ1, cyclohex-
ane/EtOAc 100/0 to 60/40; Rf =0.26 cyclohexane/EtOAc 50/
50.
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12 Selective Palladium-Catalyzed Domino Heck/Buchwald–
Hartwig Arylations of N-Glycosylcinnamamides: An
Efficient Route to 4-Aryl-N-glycosylquinolin-2-ones
Adv. Synth. Catal. 2017, 359, 1 – 12
Thi Thanh Huyen Luong, Sabrina Touchet, Mouad Alami,
Samir Messaoudi*
Adv. Synth. Catal. 0000, 000, 0 – 0
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