Stereoselective palladium-catalyzed alkenylation and alkynylation of thioglycosides

Article abstract of DOI:10.1002/adsc.201300419

An efficient and unprecedented palladium-catalyzed S-glycosylation reaction of a range of alkenyl and alkynyl halides by using thiosugars as nucleophile partners has been established. With palladium diacetate in combination with Xantphos as the catalytic system, a variety of β-alkenylthioglycosides as well as β-alkynylthioglycosides can be prepared in good to excellent yields. The efficiency of this general protocol was well-demonstrated by the formal synthesis of a leaf-closure β-glucosidase inhibitor. Copyright

Full text of DOI:10.1002/adsc.201300419

FULL PAPERS
DOI: 10.1002/adsc.201300419
Stereoselective Palladium-Catalyzed Alkenylation and
Alkynylation of Thioglycosides
Etienne Brachet,a Jean-Daniel Brion,a Mouad Alami,a,* and Samir Messaoudia,*
a
Univ Paris-Sud, CNRS, BioCIS-UMR 8076, LabEx LERMIT, Laboratoire de Chimie Thꢀrapeutique, Facultꢀ de
Pharmacie, 5 rue J.-B. Clꢀment, 92296 Chꢁtenay-Malabry, France
Fax : (+33)-1-4683-5828; e-mail: mouad.alami@u-psud.fr or samir.messaoudi@u-psud.fr
Received: May 13, 2013; Revised: July 12, 2013; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300419.
Abstract: An efficient and unprecedented palladium- good to excellent yields. The efficiency of this gener-
catalyzed S-glycosylation reaction of a range of al- al protocol was well-demonstrated by the formal syn-
kenyl and alkynyl halides by using thiosugars as nu- thesis of a leaf-closure b-glucosidase inhibitor.
cleophile partners has been established. With palladi-
um diacetate in combination with Xantphos as the
catalytic system, a variety of b-alkenylthioglycosides Keywords: b-alkenylthioglycosides; b-alkynylthiogly-
as well as b-alkynylthioglycosides can be prepared in cosides; palladium catalysis; thioglycosides
Introduction
Furthermore, alkenylthioglycosides can be valuable
precursors[4] to alkylthioglycosides, themselves of sig-
Replacement of the anomeric oxygen in oligosacchar- nificant biological importance.[5,6] Over the past
ides and other glycoconjugates with a sulfur atom decade, alkenylthioglycosides have received very little
leads to the thioglycoside family, an important class attention, and therefore their accessibility, an equally
of synthetic carbohydrates.[1] Alkenylthioglycosides if not more important issue than applications, remains
are a subfamiliy of thioglycoconjugates, whose deriva- a challenging problem. To the best of our knowledge,
tives show promising biological activities, including only one example has been reported for the synthesis
leaf-closure and irreversible glycosidase inhibitors,[2] of alkenylthioglycoside via reaction of an electrophilic
as well as precursors in melanin research biopoly- acetohaloglycoside precursor with a thioenol ether
mers[3] (Figure 1).
under basic conditions.[2a] Alternative routes consist
of the use of selenium-containing thioglycosides as an
Figure 1. Chemical structures of some bioactive alkenyl or alkyl thioglycoside derivatives.
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in situ generating free radical glycosidation reagent,[3]
As summarized in Table 1, (E)-styryl bromides in-
or by nucleophilic addition of the acetylated 1-thio- cluding 2b and 2c gave the corresponding alkenylthio-
glucose to a,b-unsaturated carbonyl compounds fol- glycoside derivatives 3b and 3c in good yields (en-
lowed by oxidation.[2b] All these multi-step procedures tries 2 and 3). Carrying out the reaction with a diaste-
however, are often moderate to low yielding, and the reomeric mixture of b-bromostyrene (E/Z 85:15), the
variety of substrates is cruelly limited. The restricted coupling proceeded stereoselectively, providing the
scope of existing protocols has prohibited a greater desired product 3d as a single E-isomer. This result
synthetic utility of alkenylthioglycosides. Therefore, suggested that either Z-isomer does not react or iso-
the search for new selective and simple procedures merizes into E-isomer. To verify this hypothesis, the
presents an interesting challenge.
coupling of 1a with Z-bromostyrene 2e was further
During our studies on metal-catalyzed C-hetero- tested. Under the optimized conditions, no reaction
ACHTUNGTRENNUNG
presence of PdACTHUNTRGNEUNG(OAc)2/Xantphos as the catalyst alkenyl iodides were further examined. Carrying out
system.[8] Herein, this versatile catalyst has been ex- the reaction with a diastereomeric mixture of b-iodos-
[9]
À
tended to C S coupling of thioglycosides with al- tyrene 2 f (E/Z 25:75) or 2g (1E,3E/1E,3Z 30:70), the
kenyl and alkynyl halides where selectivities, broad coupling proceeded stereoselectively, providing in an
tolerance to functional groups as well as practical ap- excellent yields the desired products 3f and 3g in the
plication were demonstrated.
same stereomeric E/Z ratio (entries 6 and 7). These
results suggested that, contrary to b-bromostyrenes,
both E- and Z-iodostyrene isomers displayed similar
reactivity. More interestingly, pure Z-iodostyrene such
as 2h is also a suitable coupling partner with thiogly-
Results and Discussion
Given our success with the synthesis of (hetero)ar- coside 1a furnishing efficiently and stereoselectively
ylthioglycosides, we first applied our optimal Pd-cata- b-thioglycosidated Z-alkene 3h without any thermal
À
lyzed C S coupling conditions [Pd
N
Xantphos (1.5 mol%), NEt3 (1 equiv.) in dioxane at of this cross-coupling reaction (entry 8). Noteworthy,
1008C][10] to the coupling of b-thioglucopyranose 1a Z-alkene reactants with long alkyl chains displayed
with vinyl iodide 2a (Scheme 1). We were delighted to excellent reactivity, as iodide 2i gave b-thioglycosyl
find that these conditions were efficient and gave the alkene 3i in 80% yield (entry 9). These molecules are
corresponding vinylthioglycoside 3a in an excellent still of interest and may be used as scaffolds to build
94% yield without any anomerization. Remarkably, compounds such as Glc-S-C8-APL (Figure 1). Perhaps
decreasing the temperature until 758C was sufficient the most striking feature of the reaction is its chemo-
to achieve complete conversion, providing 3a in a sim- selectivity. Halogen substituents (entry 10) were toler-
ilar yield (94%).
ated on the styryl double bond with the reaction oc-
Prompted by these results, we subsequently investi- curring efficiently (82% yield) and selectively on the
À
gated the synthesis of alkenylthioglycosides
3
C I bond. This chlorinated compound 3j of particular
(Table 1) by coupling various thioglycosides 1a–g interest, as it contains reactive handles and, as such,
(Figure 2) with a variety of (E)- and (Z)-functional- could be used as a foundation for the synthesis of
ized alkenyl halides 2a–p (Table 1). Compounds 3 more complex molecules.[11] Besides b-styryl halides,
that feature alkenyl substituents at the sulfur atom of a-styryl halides such as a-iodostyrene 2k also worked
the sugar moiety have not previously been reported, well, affording the corresponding alkenylthioglycoside
perhaps due to the difficulty in their preparation by 3k in a good yield (entry 11). Cyclic alkenyl halides
standard procedures.[2a]
such as 2l and 2m gave the corresponding thioglycosy-
lated 3l and 3m in 95% and 68% yields, respectively
Scheme 1.
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Stereoselective Palladium-Catalyzed Alkenylation and Alkynylation of Thioglycosides
Table 1. Palladium-catalyzed coupling of b-thioglycosides 1a–g with alkenyl halides 2.[a]
[a]
Reactions of 1a (0.375 mmol) with vinyl halides (0.25 mmol) were performed in a sealed Schlenk tube at 758C for 1 h in
dioxane (1.5 mL) in the presence of Pd
Yield of isolated product.
ACHTUNGTRENN(NUG OAc)2 (5 mol%), Xantphos (2.5 mol%), and Et3N (0.25 mmol).
[b]
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reaction is not effective with perbenzylated a-d-thio-
glucopyranose 1g. The coupling procedure is not lim-
ited only to monothiosaccharides but also works suc-
cessfully with peracetylated b-d-disaccharide 1f de-
rived from d-cellobiose octaacetate. The exclusive
1,2-trans b-thioglycosides 3s and 3t were obtained in
70% and 68% yields, respectively, and the stereo-
chemistry of the 1-4’ glycosidic bond remained intact
(entries 19 and 20). More interestingly, coupling of
unprotected b-d-thioglucose 1c and b-d-thiogalactose
1e with a-iodostyrene 2k under this procedure fur-
nished exclusively b-anomers 3u and 3v in good yields
without any side product resulting from O-arylation
Figure 2. Thioglycosides 1a–g used in this study.
(entries 12 and 13). Performing the C S glycosidic under Pd catalysis.[12] A literature search did not un-
À
bond forming reaction with (E)-1,2-diiodoethene 2n cover any metal-catalyzed coupling of free thioglyco-
(ratio 1a:2n=2:1) provides the bis-b-thioglycoside 3n side nucleophiles with C
in 65% yield (entry 14). In addition to the alkenyl halides evaluated above,
(sp2) alkenyl halides.
ACHTUNGTRENNUNG
In a further set of experiments, we investigated the substituted alkynyl bromides 4 were examined as
scope and generality of the method for a range of aglycone coupling partners in the thioglycosylation
mono- and dithiosaccharides 1b–f (Figure 2). As de- procedure.
picted in Table 1 (entries 15–22), coupling reactions
Alkynylated thioglycoside products 5a–e were ob-
proceeded cleanly in high yields without any signifi- tained diastereoselectively in good to excellent yields
cant side reaction such as anomerization of the result- (Scheme 2) regardless the nature of the substituent
ing alkenylthioglycosides. The reaction seems to be group on the aromatic ring of the alkynyl bromide.
general with respect to the sugar configuration as per-
Finally, the synthetic potential of this protocol was
O-acetylated 1-thio-b-d-galactose 1d gave the corre- well-illustrated by the formal synthesis of a leaf-clo-
sponding products 3o–q in good to excellent yields sure b- glucosidase inhibitor.[2a] The key step was the
(76–95%, entries 15–17). Importantly, there is no sig- coupling of 2-iodoacrylate 6 with peracetylated b-d-
nificant impact of protecting groups on the reactivity thioglucopyranose 1a under optimized conditions to
of the thiosugar derivatives since benzyl-protected give acetylated thioglycoside 7 in a good 65% yield
carbohydrate 1b reacts similarly to O-acetylated de- with exclusive b-selectivity (Scheme 3). Compound 7
rivative 1a furnishing the coupling product 3r in can be converted to the leaf-closure b-glucosidase in-
a good 73% yield (entry 18). It is noteworthy that the hibitor 8 by a known procedure.[2a]
Scheme 2. Palladium-catalyzed coupling of peracetylated b-thioglucosides 1a–e with alkynyl halides.
4
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Stereoselective Palladium-Catalyzed Alkenylation and Alkynylation of Thioglycosides
Scheme 3. Formal synthesis of leaf-movement inhibitor (8).
Palladium-Catalyzed Coupling of b-Thioglucose 1a
with Alkenyl and Alkynyl Halides (2 and 4)
Conclusions
Typical procedure: A flame-dried resealable Schlenk tube
was charged with PdACTHNUTRGNE(UNG OAc)2 (3 mol%), Xantphos
In summary, we have developed the first method to
prepare alkenylated and alkynylated thioglycoside de-
rivatives via Pd-catalyzed glycosylation of functional-
(1.5 mol%), thiosugar 1 (0.375 mmol), alkenyl or alkynyl
halide 2 or 4 (0.25 mmol), and Et3N (0.25 mmol). The
Schlenk tube was capped with a rubber septum, evacuated
and backfilled with argon; then, dioxane (1.5 mL) was
added through the septum. The septum was replaced with
a teflon screwcap. The Schlenk tube was sealed, and the
mixture was stirred at 758C for 1 h. The resulting suspension
was cooled to room temperature and filtered through celite
eluting with ethyl acetate. The filtrate was concentrated and
purification of the residue by silica gel column chromatogra-
phy gave the desired products 3 or 5.
ized alkenyl and alkynyl halides. To the best of our
2
À
À
knowledge the C
G
bonds were formed, for the first time, directly by
using thioglycosides as a nucleophile partner in the
presence of PdACHTNUTRGNEUNG(OAc)2/Xantphos as the catalyst
system. The reaction is highly diastereoselective, func-
tional-group tolerant, step-economical, and proceeds
stereoselectively in good to excellent yields with a va-
riety of Z- and E-haloalkenes. We believe that this
methodology will find broad applications in organic
synthetic chemistry as well as in the combinatorial
and pharmaceutical sciences.
Analytical Data for Alkenylthioglycosides 3
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-(vinylthio)tetrahy-
dro-2H-pyran-3,4,5-triyl triacetate (3a): yield: 97 mg
(94%); Rf =0.25 (cyclohexane:AcOEt, 7:3); white-yellow
solid; mp 95–978C; [a]2D4: À14.0 (c 1.0, CHCl3); 1H NMR
(300 MHz, CDCl3): d=6.38 (dd, J=16.8, 9.8 Hz, 1H), 5.40
(d, J=5.2 Hz, 1H), 5.35 (d, J=1.7 Hz, 1H), 5.20 (t, J=
9.3 Hz, 1H), 5.04 (td, J=9.6, 3.3 Hz, 2H), 4.59 (d, J=
10.0 Hz, 1H), 4.21 (dd, J=12.4, 5.0 Hz, 1H), 4.09 (dd, J=
12.4, 2.2 Hz, 1H), 3.72 (ddd, J=10.0, 4.9, 2.3 Hz, 1H), 2.03
(s, 3H), 2.00 (s, 3H), 1.98 (s, 3H), 1.96 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=170.59 (C=O), 170.13 (C=O), 169.37
(C=O), 169.20 (C=O), 127.36 (CH), 117.93 (CH2), 83.26
(CH), 76.10 (CH), 73.86 (CH), 69.86 (CH), 68.22 (CH),
62.10 (CH2), 20.74 (CH3), 20.66 (CH3), 20.60 (2CH3); IR
(neat): n=3452, 3394, 3148, 2170, 2144, 1756, 1738, 1590,
1433, 1366, 1247, 1206, 1092, 1030 cmÀ1; HR-MS (ESI):
m/z=413.0874, calculated for C16H22NaO9S: 413.0882.
Experimental Section
General Experimental Methods
The compounds were all identified by usual physical meth-
ods, i.e., 1H NMR, 13C NMR (J-MOD), IR, MS (ESI). 1H
and 13C NMR spectra were measured in CDCl3 or DMSO-d6
1
with a Bruker Avance-300. H chemical shifts are reported
in ppm from an internal standard TMS or of residual chloro-
form (7.27 ppm). The following abreviation are used: m
(multiplet), s (singlet), bs (broad singlet), d (doublet), t
(triplet) dd (doublet of doublet), td (triplet of doublet), q
(quadruplet), qui (quintuplet), sex (sextuplet). 13C chemical
shifts are reported in ppm from the central peak of deuter-
iochloroform (77.14 ppm). IR spectra were measured on
a Bruker Vector 22 spectrophotometer. MS were recorded
on a Micromass spectrometer. Analytical TLC was per-
formed on Merck precoated silica gel 60F plates. Merck
silica gel 60 (0.015–0.040 mm) was used for column chroma-
tography. Melting points were recorded on a Bꢃchi B-450
apparatus and are uncorrected.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-[(E)-4-meth-
oxystyrylthio]tetrahydro-2H-pyran-3,4,5-triyl
triacetate
(3b): yield: 95 mg (75%); Rf =0.57 (cyclohexane:AcOEt,
5:5); white-yellow solid; mp 141–1438C; [a]2D4: À26.0 (c 1.0,
1
CHCl3); H NMR (300 MHz, CDCl3): d=7.28 (d, J=9.3 Hz,
2H), 6.84 (d, J=8.7 Hz, 2H), 6.74 (d, J=15.4 Hz, 1H), 6.57
(d, J=15.4 Hz, 1H), 5.24 (dd, J=10.3, 8.2 Hz, 1H), 5.10 (td,
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J=9.6, 5.8 Hz, 2H), 4.60 (d, J=9.9 Hz, 1H), 4.25 (dd, J=
12.4, 4.8 Hz, 1H), 4.16 (dd, J=12.4, 2.3 Hz, 1H), 3.80 (s,
3H), 3.76 (ddd, J=10.0, 4.9, 2.4 Hz, 1H), 2.06 (s, 3H), 2.05
(s, 3H), 2.02 (s, 3H), 1.99 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=170.75 (C=O), 170.29 (C=O), 169.49 (C=O),
169.35 (C=O), 159.76 (CH), 135.93 (C), 129.23 (2CH),
127.73 (CH), 115.11 (2CH), 114.24 (CH), 83.92 (CH), 76.22
(CH), 74.03 (CH), 70.03 (CH), 68.34 (CH), 62.21 (CH2),
55.43 (CH3), 20.81 (2CH3), 20.68 (2CH3); IR (neat): n=
3459, 2245, 2015, 1755, 1739, 1606, 1511, 1467, 1366, 1251,
1209, 1175, 1129, 1090 cmÀ1; HR-MS (ESI): m/z=519.1282,
calculated for C23H28NaO10S: 519.1295.
(CH3), 20.81 (CH3), 20.66 (CH3); 1H NMR (300 MHz,
CDCl3, E isomer): d=7.28 (d, J=9.3 Hz, 2H), 6.84 (d, J=
8.7 Hz, 2H), 6.74 (d, J=15.4 Hz, 1H), 6.57 (d, J=15.4 Hz,
1H), 5.24 (dd, J=10.3, 8.2 Hz, 1H), 5.10 (td, J=9.6, 5.8 Hz,
2H), 4.60 (d, J=9.9 Hz, 1H), 4.25 (dd, J=12.4, 4.8 Hz, 1H),
4.16 (dd, J=12.4, 2.3 Hz, 1H), 3.80 (s, 3H), 3.76 (ddd, J=
10.0, 4.9, 2.4 Hz, 1H), 2.06 (s, 3H), 2.05 (s, 3H), 2.02 (s,
3H), 1.99 (s, 3H); 13C NMR (75 MHz, CDCl3): d=170.75
(C=O), 170.29 (C=O), 169.49 (C=O), 169.35 (C=O), 159.76
(CH), 135.93 (C), 129.23 (2CH), 127.73 (CH), 115.11
(2CH), 114.24 (CH), 83.92 (CH), 76.22 (CH), 74.03 (CH),
70.03 (CH), 68.34 (CH), 62.21 (CH2), 55.43 (CH3), 20.81
(2CH3), 20.68 (2CH3); HR-MS (ESI): m/z=519.1284, calcu-
lated for C23H28NaO10S: 519.1295.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-{[(3E)-4-phenyl-
buta-1,3-dien-1-yl]thio}tetrahydro-2H-pyran-3,4,5-triyl tri-
acetate (3g): yield: 103 mg (89%); Rf =0.54 (cyclohexane:A-
cOEt, 5:5); white-yellow solid; mp 86–888C; [a]2D4: À10.0 (c
1.0, CHCl3); mixture 1E,3E/1E,3Z (30:70); 1H NMR
(300 MHz, CDCl3, Z isomer): d=7.40 (m, 2H), 7.30 (m,
2H), 7.22 (m, 1H), 7.00 (dd, J=10.8, 15.5 Hz, 1H), 6.58 (d,
J=15.5 Hz, 1H), 6.47 (dd, J=9.4, 10.8 Hz, 1H), 6.16 (d, J=
9.4 Hz, 1H), 5.23 (m, 1H), 5.12 (m, 1H), 5.11 (m, 1H), 4.63
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-{[(E)-2-chloro-
styryl]thio}tetrahydro-2H-pyran-3,4,5-triyl triacetate (3c):
yield: 81 mg (65%); Rf =0.68 (cyclohexane:AcOEt, 5:5);
white-yellow solid; mp 64–668C; [a]2D4: À176.0 (c 1.0,
CHCl3); 1H NMR (300 MHz, CDCl3): d=7.47 (dd, J=7.5,
1.9 Hz, 1H), 7.33 (dd, J=7.6, 1.6 Hz, 1H), 7.25–7.12 (m,
2H), 7.08 (d, J=15.6 Hz, 1H), 6.78 (d, J=15.6 Hz, 1H),
5.26 (t, J=9.3 Hz, 1H), 5.13 (td, J=9.6, 7.3 Hz, 2H), 4.72
(d, J=9.9 Hz, 1H), 4.27 (dd, J=12.4, 4.9 Hz, 1H), 4.16 (dd,
J=12.4, 2.2 Hz, 1H), 3.80 (ddd, J=10.0, 4.8, 2.3 Hz, 1H),
2.06 (s, 3H), 2.04 (s, 3H), 2.02 (s, 3H), 2.00 (s, 3H);
13C NMR (75 MHz, CDCl3): d=170.71 (C=O), 170.22 (C= (m, 1H), 4.26 (dd, J=12.4, 4.8 Hz, 1H), 4.13 (dd, J=12.4,
O), 169.45 (C=O), 169.31 (C=O), 134.49 (C), 132.65 (C),
129.91 (CH), 128.99 (CH), 128.89 (CH), 127.05 (CH), 126.68
(CH), 122.03 (CH), 83.60 (CH), 76.32 (CH), 73.92 (CH),
69.92 (CH), 68.24 (CH), 62.13 (CH2), 20.78 (CH3), 20.74
(CH3), 20.66 (2CH3); IR (neat): n=3474, 2203, 1755, 1739,
1593, 1365, 1208, 1091, 1032, 955 cmÀ1; HR-MS (ESI): m/z=
523.0784, calculated for C22H25ClNaO9S: 523.0800.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-[(E)-styrylthio]-
tetrahydro-2H-pyran-3,4,5-triyl triacetate (3d): yield:
85 mg (73%); Rf =0.29 (cyclohexane:AcOEt, 7:3); white-
yellow solid; mp 113–1158C; [a]2D4: À160.0 (c 1.0, CHCl3);
1H NMR (300 MHz, CDCl3): d=7.39–7.18 (m, 5H), 6.75 (s,
2H), 5.25 (t, J=9.3 Hz, 1H), 5.11 (m, 2H), 4.65 (d, J=
9.9 Hz, 1H), 4.26 (dd, J=12.4, 4.9 Hz, 1H), 4.16 (dd, J=
12.4, 2.3 Hz, 1H), 3.78 (ddd, J=10.0, 4.9, 2.4 Hz, 1H), 2.06
(s, 3H), 2.05 (s, 3H), 2.02 (s, 3H), 2.00 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=170.70 (C=O), 170.24 (C=O), 169.46
(C=O), 169.31 (C=O), 136.35 (C), 134.93 (CH), 128.79
(CH), 128.40 (2CH), 128.09 (CH), 126.33 (2CH), 118.33
(CH), 83.75 (CH), 76.26 (CH), 73.96 (CH), 70.05 (CH),
68.31 (CH), 62.20 (CH2), 20.79 (2CH3), 20.69 (2CH3); IR
(neat): n=3438, 3386, 3356, 3301, 3252, 2526, 2253, 2159,
2025, 1946, 1756, 1217, 1037 cmÀ1; HR-MS (ESI): m/z=
489.1182, calculated for C22H26NaO9S: 489.1190.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-[(4-methoxystyr-
yl)thio]tetrahydro-2H-pyran-3,4,5-triyl triacetate (3f):
yield: 125 mg (97%); Rf =0.57 (cyclohexane:AcOEt, 5:5);
white-yellow oil; [a]24: +40.0 (c 1.0, CHCl3); 1H NMR
(300 MHz, CDCl3, Z Disomer): d=7.33 (d, J=8.6 Hz, 2H),
6.85 (d, J=8.6 Hz, 2H), 6.56 (d, J=10.7 Hz, 1H), 6.21 (d,
J=10.7 Hz, 1H), 5.33–5.01 (m, 3H), 4.63 (d, J=10.0 Hz,
1H), 4.27 (dd, J=12.4, 4.8 Hz, 1H), 4.13 (dd, J=12.4,
1.8 Hz, 1H), 3.79 (s, 3H), 3.77–3.72 (m, 1H), 2.07 (s, 3H),
2.02 (s, 3H), 1.99 (s, 3H), 1.97 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=170.72 (C=O), 170.25 (C=O), 169.43 (C=O),
169.26 (C=O), 158.86 (C), 130.26 (2CH), 129.04 (C), 128.95
(CH), 117.78 (CH), 113.81 (2CH), 84.78 (CH), 76.34 (CH),
73.97 (CH), 70.11 (CH), 68.21 (CH), 62.11 (CH2), 55.35
2.2 Hz, 1H), 2.06 (s, 3H), 2.04 (s, 3H), 2.02 (s, 3H), 2.00 (s,
3H); 13C NMR (75 MHz, CDCl3, Z isomer): d=170.71 (C=
O), 170.25 (C=O), 169.44 (C=O), 169.27 (C=O), 137.01 (C),
134.55 (CH), 131.99 (CH), 128.07 (CH), 126.73 (2CH),
124.03 (CH), 123.74 (2CH), 120.08 (CH), 83.79 (CH), 76.30
(CH), 73.95 (CH), 70.20 (CH), 63.21 (CH), 62.10 (CH2),
20.80 (CH3), 20.74 (CH3), 20.66 (2CH3); 1H NMR
(300 MHz, CDCl3, E isomer): d=7.40 (m, 2H), 7.30 (m,
2H), 7.22 (m, 1H), 6.58 (d, J=15.5 Hz, 1H), 6.53 (m, 1H),
6.36 (m, 1H), 5.23 (m, 1H), 5.12 (m, 1H), 5.11 (m, 1H),
4.63 (m, 1H), 4.26 (dd, J=12.4, 4.8 Hz, 1H), 4.13 (dd, J=
12.4, 2.2 Hz, 1H), 2.06 (s, 3H), 2.04 (s, 3H), 2.02 (s, 3H),
2.00 (s, 3H); 13C NMR (75 MHz, CDCl3, E isomer): d=
170.71 (C=O), 170.25 (C=O), 169.44 (C=O), 169.27 (C=O),
137.01 (C), 134.55 (CH), 131.99 (CH), 128.07 (CH), 126.73
(2CH), 124.03 (CH), 123.74 (2CH), 121.48 (CH), 83.79
(CH), 76.30 (CH), 73.95 (CH), 70.20 (CH), 63.21 (CH),
62.10 (CH2), 20.80 (CH3), 20.74 (CH3), 20.66 (2CH3); IR
(neat): n=3309, 3134, 2358, 2135, 1755, 1740, 1711, 1365,
1247, 1211, 1091, 1033 cmÀ1; HR-MS (ESI): m/z=515.1333,
calculated for C24H28NaO9S: 515.1346.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-[(3-fluoro-4-me-
thoxystyryl)thio]tetrahydro-2H-pyran-3,4,5-triyl triacetate
(3h): yield: 115 mg (90%); Rf =0.55 (cyclohexane:AcOEt,
5:5); white-yellow solid; mp 143–1458C; [a]2D4: +26.0 (c 1.0,
1
CHCl3); H NMR (300 MHz, CDCl3): d=7.17 (dd, J=12.7,
2.1 Hz, 1H), 7.09 (d, J=8.5 Hz, 1H), 6.90 (t, J=8.6 Hz,
1H), 6.48 (d, J=10.8 Hz, 1H), 6.27 (d, J=10.8 Hz, 1H),
5.34–5.02 (m, 3H), 4.63 (d, J=9.8 Hz, 1H), 4.26 (dd, J=
12.5, 4.7 Hz, 1H), 4.18–4.07 (m, 1H), 3.86 (s, 3H), 3.76 (ddd,
J=9.8, 4.6, 2.2 Hz, 1H), 2.06 (s, 3H), 2.01 (s, 3H), 1.98 (s,
3H), 1.98 (s, 3H); 13C NMR (75 MHz, CDCl3): d=170.66
(C=O), 170.18 (C=O), 169.39 (C=O), 169.19 (C=O), 151.97
(C, d, J=245.4 Hz), 146.87 (C, d, J=10.8 Hz), 129.59 (C, d,
J=6.7 Hz), 127.92 (CH), 125.12 (CH, d, J=2.9 Hz), 119.29
(CH), 116.33 (CH, d, J=19.1 Hz), 113.12 (CH), 84.21 (CH),
76.37 (CH), 73.89 (CH), 70.05 (CH), 68.14 (CH), 62.05
(CH2), 56.30 (CH), 20.77 (CH3), 20.61 (3CH3); 19F NMR
6
asc.wiley-vch.de
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Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
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Stereoselective Palladium-Catalyzed Alkenylation and Alkynylation of Thioglycosides
(188 MHz, CDCl3): d=À133.31 (s); IR (neat): n=3375,
2139, 2006, 1754, 1740, 1513, 1285, 1209, 1120, 1032 cmÀ1
HR-MS (ESI): m/z=537.1191, calculated for
C23H27FNaO10S: 537.1201.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-{[(Z)-hex-1-en-
J=7.3, 1.5 Hz, 1H), 6.89 (d, J=0.6 Hz, 1H), 5.25 (t, J=
;
9.3 Hz, 1H), 5.07 (ddd, J=16.2, 9.4, 6.8 Hz, 2H), 4.77 (d, J=
10.0 Hz, 1H), 4.27–4.13 (m, 2H), 3.77 (ddd, J=10.0, 5.0,
2.7 Hz, 1H), 3.65–3.45 (m, 2H), 2.06 (s, 3H), 2.05 (s, 3H),
2.02 (s, 3H), 1.99 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
170.53 (C=O), 170.17 (C=O), 169.41 (C=O), 169.30 (C=O),
144.16 (C), 143.44 (C), 136.90 (C), 133.64 (CH), 126.72
(CH), 124.91 (CH), 123.32 (CH), 120.48 (CH), 84.17 (CH),
76.01 (CH), 73.88 (CH), 70.01 (CH), 68.29 (CH), 62.26
(CH2), 43.74 (CH2), 20.74 (2CH3), 20.61 (2CH3); IR (neat):
n=3378, 3307, 3065, 2559, 2364, 2164, 2093, 2007, 1755,
1513, 1366, 1213, 1121, 1060, 1033 cmÀ1; HR-MS (ESI):
m/z=501.1175, calculated for C23H26NaO9S: 501.1190.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-[(6-oxocyclo-
hex-1-en-1-yl)thio]tetrahydro-2H-pyran-3,4,5-triyl triace-
tate (3m): yield: 78 mg (68%); Rf =0.45 (cyclohexane:A-
cOEt, 5:5); white-yellow oil; [a]2D4: À40.0 (c 1.0, CHCl3);
1H NMR (300 MHz, CDCl3): d=7.23 (t, J=4.3 Hz, 1H),
5.23 (t, J=9.3 Hz, 1H), 5.06 (td, J=9.6, 3.3 Hz, 2H), 4.78
(d, J=10.0 Hz, 1H), 4.20 (dd, J=12.3, 5.0 Hz, 1H), 4.12 (dd,
J=12.3, 2.4 Hz, 1H), 3.70 (ddd, J=10.1, 5.1, 2.5 Hz, 1H),
2.52 (dt, J=16.7, 5.7 Hz, 3H), 2.09 (m, 3H), 2.07 (s, 3H),
2.05 (s, 3H), 2.02 (s, 3H), 2.00 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=195.24 (C=O), 170.60 (C=O), 170.24 (C=O),
169.56 (C=O), 151.08 (CH), 132.71 (C), 82.63 (CH), 76.03
(CH), 74.09 (CH), 69.64 (CH), 68.44 (CH), 62.32 (CH2),
38.67 (CH2), 27.75 (CH2), 22.60 (CH2), 20.83 (2CH3), 20.72
(2CH3); IR (neat): n=3451, 3068, 2262, 2123, 2050, 1979,
1752, 1368, 1215 cmÀ1; HR-MS (ESI): m/z=481.1164, calcu-
lated for C20H26NaO10S: 481.1139.
1-yl]thio}tetrahydro-2H-pyran-3,4,5-triyl triacetate (3i):
yield: 100 mg (80%); Rf =0.53 (cyclohexane:AcOEt, 6:4);
white-yellow solid; mp 85–878C; [a]2D4: +13.0 (c 1.0, CHCl3);
1H NMR (300 MHz, CDCl3): d=6.03 (d, J=9.3 Hz, 1H),
5.75 (dt, J=9.2, 7.2 Hz, 1H), 5.19 (t, J=9.3 Hz, 1H), 5.06
(td, J=9.6, 5.4 Hz, 2H), 4.52 (d, J=9.9 Hz, 1H), 4.23 (dd,
J=12.4, 4.8 Hz, 1H), 4.10 (dd, J=12.4, 2.3 Hz, 1H), 3.71
(ddd, J=10.0, 4.7, 2.4 Hz, 1H), 2.05 (s, 3H), 2.02 (s, 3H),
1.99 (s, 3H), 1.97 (s, 3H), 1.40–1.14 (m, 6H), 0.85 (t, J=
7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3): d=170.68 (C=O),
170.23 (C=O), 169.42 (C=O), 169.21 (C=O), 134.79 (CH),
118.11 (CH), 83.54 (CH), 76.16 (CH), 74.01 (CH), 70.17
(CH), 68.27 (CH), 62.15 (CH2), 30.95 (CH2), 28.95 (CH2),
22.30 (CH2), 20.77 (CH3), 20.69 (CH3), 20.64 (2CH3), 13.94
(CH3); IR (neat): n=3449, 2961, 2362, 2167, 1756, 1740,
1366, 1210, 1093 cmÀ1; HR-MS (ESI): m/z=469.1505, calcu-
lated for C20H30NaO9S: 469.1503.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-{[(Z)-2-chloro-
2-phenylvinyl]thio}tetrahydro-2H-pyran-3,4,5-triyl triace-
tate (3j): yield: 101 mg (82%); Rf =0.43 (cyclohexane:A-
cOEt, 6:4); white-yellow solid; mp 148–1508C; [a]2D4: À61.0
1
(c 1.0, CHCl3); H NMR (300 MHz,): d=7.58–7.46 (m, 2H),
7.40–7.23 (m, 3H), 6.79 (s, 1H), 5.19 (dq, J=27.6, 9.2 Hz,
3H), 4.72 (d, J=9.8 Hz, 1H), 4.25 (dd, J=12.4, 4.9 Hz, 1H),
4.14 (dd, J=12.4, 2.1 Hz, 1H), 3.79 (ddd, J=10.0, 4.6,
2.2 Hz, 1H), 2.05 (s, 3H), 2.05 (s, 3H), 2.02 (s, 3H), 2.00 (s,
3H); 13C NMR (75 MHz, CDCl3): d=170.60 (C=O), 170.15
(C=O), 169.41 (C=O), 169.20 (C=O), 136.85 (C), 131.50 (C),
128.74 (CH), 128.53 (2CH), 125.96 (2CH), 118.13 (CH),
82.52 (CH), 76.47 (CH), 73.78 (CH), 70.15 (CH), 68.16
(CH), 62.07 (CH2), 20.74 (CH3), 20.62 (3CH3); IR (neat):
n=3375, 3192, 2362, 2145, 2029, 1970, 1757, 1740, 1711,
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-{[(E)-2-
{[(2R,3S,4R,5S,6S)-3,4,5-triacetoxy-6-(acetoxymethyl)te-
trahydro-2H-pyran-2-yl]thio}vinyl]thio}tetrahydro-2H-
pyran-3,4,5-triyl triacetate (3n): yield: 122 mg (65%); Rf =
0.40 (cyclohexane:AcOEt, 5:5); white-yellow solid; mp 82–
848C; [a]2D4: +30.0 (c 1.0, CHCl3); 1H NMR (300 MHz,
CDCl3): d=6.46 (s, 2H), 5.16 (tt, J=11.7, 9.2 Hz, 6H), 4.53
(d, J=9.6 Hz, 2H), 4.27 (dd, J=12.5, 4.7 Hz, 2H), 4.17 (dd,
J=12.4, 2.2 Hz, 2H), 3.76 (ddd, J=9.4, 4.4, 2.2 Hz, 2H),
2.08 (s, 6H), 2.04 (s, 6H), 2.01 (s, 6H), 1.98 (s, 6H);
13C NMR (75 MHz, CDCl3): d=170.75 (2C=O), 170.27
(2C=O), 169.42 (2C=O), 169.18 (2C=O), 124.71 (2CH),
83.56 (2CH), 76.33 (2CH), 73.98 (2CH), 69.86 (2CH), 68.14
(2CH), 62.04 (2CH2), 20.88 (2CH3), 20.78 (2CH3), 20.68
(4CH3); IR (neat): n=3426, 3184, 3112, 2356, 2335, 2149,
1364, 1206, 1090, 1060 cm<M->1
; HR-MS (ESI): m/z=
523.0798, calculated for C22H25ClNaO9S: 523.0800.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-{[1-(3,4,5-trime-
thoxyphenyl)vinyl]thio}tetrahydro-2H-pyran-3,4,5-triyl tri-
acetate (3k): yield: 105 mg (76%); Rf =0.47 (cyclohexane:A-
cOEt, 5:5); white-yellow solid; mp 44–468C; [a]2D4: À71.0 (c
1
1.0, CHCl3); H NMR (300 MHz, CDCl3): d=6.74 (s, 2H),
5.54 (s, 1H), 5.49 (s, 1H), 5.22–4.97 (m, 4H), 4.61 (d, J=
9.8 Hz, 1H), 4.17 (dd, J=12.4, 5.0 Hz, 1H), 4.04 (dd, J=
12.3, 2.2 Hz, 1H), 3.85 (s, 6H), 3.84 (s, 3H), 3.60–3.50 (m,
1H), 2.04 (s, 6H), 1.97 (s, 6H); 13C NMR (75 MHz, CDCl3):
d=170.58 (C=O), 170.20 (C=O), 169.39 (C=O), 169.22 (C=
O), 153.06 (2C), 142.25 (C), 138.78 (C), 134.26 (C), 116.45
(CH2), 104.95 (2CH), 84.32 (CH), 75.92 (CH), 73.97 (CH),
70.11 (CH), 68.25 (CH), 62.12 (CH2), 60.96 (CH3), 56.23
(2CH3), 20.72 (2CH3), 20.64 (CH3), 20.61 (CH3); IR (neat):
n=3411, 3181, 3090, 2944, 2511, 2182, 2029, 1987, 1756,
1578, 1504, 1412, 1366, 1323, 1214 cmÀ1; HR-MS (ESI):
m/z=579.1497, calculated for C25H32NaO12S: 579.1507.
(2S,3R,4S,5R,6R)-2-[(1H-inden-2-yl)thio]-6-(acetoxy-
methyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (3l):
yield: 113 mg (95%); Rf =0.46 (cyclohexane:AcOEt, 6:4);
white-yellow solid; mp 139–1418C; [a]2D4: À31.0 (c 1.0,
2012, 1755, 1738, 1711, 1431, 1365, 1248, 1204, 1092 cmÀ1
HR-MS (ESI): m/z=775.1556, calculated for
C30H40NaO18S2: 775.1548.
(2S,3R,4S,5S,6R)-2-[(1H-Inden-2-yl)thio]-6-(acetoxy-
;
methyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (3o):
yield: 113 mg (95%); Rf =0.46 (cyclohexane:AcOEt, 6:4);
white-yellow solid; mp 132–1348C; [a]2D4: À30.0 (c 1.0,
1
CHCl3); H NMR (300 MHz, CDCl3): d=7.36 (d, J=7.3 Hz,
1H), 7.31–7.18 (m, 2H), 7.14 (dd, J=10.2, 4.3 Hz, 1H), 6.90
(s, 1H), 5.44 (d, J=3.1 Hz, 1H), 5.32 (t, J=9.9 Hz, 1H),
5.27 (s, 1H), 5.08 (dd, J=9.9, 3.3 Hz, 1H), 4.76 (d, J=
9.9 Hz, 1H), 4.25–4.09 (m, 2H), 3.99 (t, J=6.4 Hz, 1H),
3.70–3.41 (m, 2H), 2.10 (s, 3H), 2.07 (s, 3H), 2.03 (s, 3H),
1.96 (s, 3H); 13C NMR (75 MHz, CDCl3): d=170.35 (C=O),
170.11 (C=O), 170.02 (C=O), 169.41 (C=O), 144.23 (C),
143.30 (C), 137.37 (C), 132.77 (CH), 126.67 (CH), 124.74
(CH), 123.24 (CH), 120.29 (CH), 84.55 (CH), 74.72 (CH),
1
CHCl3); H NMR (300 MHz, CDCl3): d=7.36 (d, J=7.3 Hz,
1H), 7.32–7.27 (m, 1H), 7.22 (d, J=7.4 Hz, 1H), 7.14 (td,
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
7
ÞÞ
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Etienne Brachet et al.
FULL PAPERS
71.95 (CH), 67.34 (CH), 67.19 (CH), 61.88 (CH2), 43.48
(CH2), 20.81 (CH3), 20.68 (CH3), 20.64 (CH3), 20.58 (CH3);
IR (neat): n=3428, 3300, 3051, 2358, 2208, 2181, 2146, 1752,
1457, 1245, 1219, 1085, 1058 cmÀ1; HR-MS (ESI): m/z=
501.1190, calculated for C23H26NaO9S: 501.1190.
(d, J=15.8 Hz, 1H), 6.77 (d, J=15.8 Hz, 1H), 4.99–4.77 (m,
6H), 4.69 (d, J=11.2 Hz, 1H), 4.59 (m, 2H), 3.87–3.56 (m,
6H); 13C NMR (75 MHz, acetone): d=139.91 (C), 139.67
(C), 139.62 (C), 139.46 (C), 137.92 (C), 130.93 (CH), 129.49
(CH), 129.09 (13CH), 129.02 (CH), 128.84 (CH), 128.68
(CH), 128.48 (2CH), 128.38 (2CH), 128.23 (2CH), 128.04
(CH), 126.71 (CH), 122.61 (CH), 87.32 (CH), 85.33 (CH),
82.21 (CH), 80.14 (CH), 78.87 (CH), 76.04 (CH2), 75.63
(CH2), 75.43 (CH2), 73.83 (CH2), 70.00 (CH2); IR (neat): n=
3339, 3068, 2366, 2148, 1998, 1947, 1600, 1496, 1361, 1210,
1157, 1090 cmÀ1; HR-MS (ESI): m/z=681.2627, calculated
for C42H42NaO5S: 681.2645.
(2R,3S,4S,5R,6S)-2-(Acetoxymethyl)-6-{[(3E)-4-phenyl-
buta-1,3-dien-1-yl]thio}tetrahydro-2H-pyran-3,4,5-triyl tri-
acetate (3p): yield: 110 mg (89%); Rf =0.62 (cyclohexane:A-
cOEt, 5:5); white-yellow oil; [a]2D4: +22.0 (c 1.0, CHCl3);
mixture 1E,3E/1E,3Z (30:70); 1H NMR (300 MHz, CDCl3,
Z isomer): d=7.39 (m, 2H), 7.30 (m, 2H), 7.21 (m, 1H),
6.99 (dd, J=11.0, 15.6 Hz, 1H), 6.57 (d, J=15.6 Hz, 1H),
6.44 (dd, J=9.4, 11.0 Hz, 1H), 6.18 (d, J=9.4 Hz, 1H), 5.44
(d, J=3.2 Hz, 1H), 5.34 (t, J=9.8 Hz, 1H), 5.07 (dd, J=
10.0, 3.4 Hz, 1H), 4.62 (dd, J=9.4, 3.9 Hz, 1H), 4.14 (dd, J=
6.5, 3.9 Hz, 2H), 4.04–3.92 (m, 1H), 2.16 (s, 3H), 2.05 (s,
3H), 2.03 (s, 3H), 1.97 (s, 3H); 13C NMR (75 MHz, CDCl3,
Z isomer): d=170.39 (C=O), 170.23 (C=O), 170.06 (C=O),
169.39 (C=O), 137.02 (C), 134.25 (CH), 131.02 (CH), 128.70
(2CH), 127.98 (CH), 126.67 (2CH), 124.04 (CH), 120.78
(CH), 84.27 (CH), 74.83 (CH), 71.90 (CH), 67.51 (CH),
67.26 (CH), 61.40 (CH2), 20.80 (CH3), 20.71 (2CH3), 20.61
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-
{[(2R,3R,5R,6S)-4,5-diacetoxy-2-(acetoxymethyl)-6-{[(Z)-
3-fluoro-4-methoxystyryl]thio}tetrahydro-2H-pyran-3-
yl]oxy}tetrahydro-2H-pyran-3,4,5-triyl
triacetate
(3s):
yield: 140 mg (70%); Rf =0.32 (cyclohexane:AcOEt, 5:5);
white-yellow solid; mp 210–2128C; [a]2D4: À10.0 (c 1.0,
1
CHCl3); H NMR (300 MHz, CDCl3): d=7.19 (dd, J=12.7,
2.1 Hz, 1H), 7.09 (m, 1H), 6.91 (t, J=8.7 Hz, 1H), 6.48 (d,
J=10.7 Hz, 1H), 6.24 (d, J=10.8 Hz, 1H), 5.26–5.01 (m,
4H), 4.96–4.87 (m, 1H), 4.61 (d, J=9.8 Hz, 1H), 4.49 (dd,
J=10.5, 4.7 Hz, 2H), 4.37 (dd, J=12.5, 4.3 Hz, 1H), 4.11
(dd, J=12.1, 5.1 Hz, 1H), 4.04 (dd, J=12.4, 2.1 Hz, 1H),
3.88 (s, 3H), 3.80 (d, J=9.1 Hz, 1H), 3.72–3.58 (m, 2H),
2.12 (s, 3H), 2.08 (s, 3H), 2.03 (s, 3H), 2.02 (s, 3H), 2.00 (s,
3H), 1.99 (s, 3H), 1.97 (s, 3H); 13C NMR (75 MHz, CDCl3):
d=170.60 (C=O), 170.40 (C=O), 170.32 (C=O), 169.86 (C=
O), 169.54 (C=O), 169.43 (C=O), 169.19 (C=O), 151.99 (d,
1
(CH3); H NMR (300 MHz, CDCl3, E isomer): d=7.39 (m,
2H), 7.30 (m, 2H), 7.21 (m, 1H), 6.76 (dd, J=10.5, 15.6 Hz,
1H), 6.54 (dd, J=10.5, 14.9 Hz, 1H),6.49 (d, J=15.6 Hz,
1H), 6.38 (d, J=14.9 Hz, 1H), 5.44 (d, J=3.2 Hz, 1H), 5.34
(t, J=9.8 Hz, 1H), 5.07 (dd, J=10.0, 3.4 Hz, 1H), 4.62 (dd,
J=9.4, 3.9 Hz, 1H), 4.14 (dd, J=6.5, 3.9 Hz, 2H), 4.04–3.92
(m, 1H), 2.16 (s, 3H), 2.05 (s, 3H), 2.03 (s, 3H), 1.97 (s,
3H); 13C NMR (75 MHz, CDCl3, E isomer): d=170.39 (C= J=243.7 Hz, C), 147.04 (d, J=30.0 Hz, C), 129.64 (d, J=
O), 170.23 (C=O), 170.06 (C=O), 169.39 (C=O), 137.02 (C),
132.34 (CH), 131.02 (CH), 128.70 (2CH), 127.98 (CH),
127.48 (CH), 126.67 (2CH),122.24 (CH), 84.27 (CH), 74.83
(CH), 71.90 (CH), 67.51 (CH), 67.26 (CH), 61.40 (CH2),
20.80 (CH3), 20.71 (2CH3), 20.61 (CH3); IR (neat): n=3460,
3298, 3149, 2929, 2369, 2328, 2192, 2032, 1751, 1370, 1219,
1086, 917 cmÀ1; HR-MS (ESI): m/z=515.1332, calculated
for C24H28NaO9S: 515.1346.
(2R,3S,4S,5R,6S)-2-(Acetoxymethyl)-6-[(1-methyl-4-
oxo-1,4-dihydroquinolin-3-yl)thio]tetrahydro-2H-pyran-
3,4,5-triyl triacetate (3q): yield: 99 mg (76%); Rf =0.22 (cy-
clohexane:AcOEt, 2:8); white-yellow solid; mp 85–878C;
[a]2D4: À111.0 (c 1.0, CHCl3); 1H NMR (300 MHz, CDCl3):
d=8.45 (d, J=8.0 Hz, 1H), 7.99 (s, 1H), 7.69 (t, J=7.4 Hz,
1H), 7.42 (dd, J=12.2, 5.7 Hz, 2H), 5.40 (d, J=3.0 Hz, 1H),
5.25 (t, J=9.9 Hz, 1H), 5.05 (dd, J=9.9, 3.3 Hz, 2H), 4.12
(ddd, J=14.3, 9.8, 6.8 Hz, 2H), 3.97 (dd, J=11.2, 6.8 Hz,
1H), 3.82 (s, 3H), 2.16 (s, 3H), 2.12 (s, 3H), 1.96 (s, 3H),
1.83 (s, 3H); 13C NMR (75 MHz, CDCl3): d=175.95 (C=O),
170.29 (C=O), 170.03 (C=O), 149.10 (CH), 140.39 (C),
132.60 (CH), 127.45 (CH), 126.43 (C), 124.76 (CH), 115.54
(CH), 109.89 (C), 83.39 (CH), 74.43 (CH), 72.07 (CH), 67.83
(CH), 67.48 (CH), 61.24 (CH2), 40.89 (CH3), 21.10 (CH3),
20.78 (CH3), 20.67 (CH3), 20.56 (CH3); IR (neat): n=3324,
3264, 3178, 2335, 1745, 1621, 1548, 1621, 1548, 1499, 1367,
1219, 1084 cmÀ1; HR-MS (ESI): m/z=544.1271, calculated
for C24H27NNaO10S: 544.1253.
3.7 Hz, C), 127.84 (CH), 125.16 (d, J=2.9 Hz, CH), 119.56
(CH), 116.40 (d, J=19.3 Hz, CH), 113.16 (CH), 100.96
(CH), 84.29 (CH), 77.30 (CH), 76.33 (CH), 73.62 (CH),
73.06 (CH), 72.17 (CH), 71.75 (CH), 70.41 (CH), 67.92
(CH), 62.19 (CH2), 61.69 (CH2), 56.38 (CH3), 20.96 (CH3),
20.78 (CH3), 20.65 (5CH3); 19F NMR (188 MHz, CDCl3):
d=À133.26; IR (neat): n=2359, 1739, 1619, 1433, 1323,
1261, 1210, 1119, 1020, 963 cmÀ1; HR-MS (ESI): m/z=
825.2056, calculated for C35H43FNaO18S: 825.2046.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-
{[(2R,3R,5R,6S)-4,5-diacetoxy-2-(acetoxymethyl)-6-{[(E)-
styryl]thio}tetrahydro-2H-pyran-3-yl]oxy}tetrahydro-2H-
pyran-3,4,5-triyl triacetate (3t): yield: 128 mg (68%); Rf =
0.38 (cyclohexane:AcOEt, 5:5); white-yellow solid; mp 208–
2108C; [a]2D4: À20.0 (c 1.0, CDCl3); 1H NMR (300 MHz,
CDCl3): d=7.36–7.11 (m, 6H), 6.67 (d, J=1.9 Hz, 1H),
5.24–4.91 (m, 4H), 4.90–4.80 (m, 1H), 4.55 (d, J=9.9 Hz,
1H), 4.45 (dd, J=9.0, 4.5 Hz, 2H), 4.31 (dd, J=12.5, 4.2 Hz,
1H), 4.05 (dd, J=12.1, 5.1 Hz, 1H), 3.97 (dd, J=12.4,
2.0 Hz, 1H), 3.72 (t, J=9.4 Hz, 1H), 3.66–3.54 (m, 2H), 2.01
(s, 3H), 2.01 (s, 3H), 1.99 (s, 3H), 1.96 (s, 3H), 1.95 (s, 3H),
1.94 (s, 3H), 1.91 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
170.55 (C=O), 170.36 (C=O), 170.29 (C=O), 169.82 (C=O),
169.57 (C=O), 169.38 (C=O), 169.15 (C=O), 136.39 (C),
134.98 (CH), 128.77 (2CH), 128.06 (CH), 126.29 (2CH),
118.40 (CH), 100.93 (CH), 83.50 (CH), 77.12 (CH), 76.42
(CH), 73.56 (CH), 73.03 (CH), 72.12 (CH), 71.71 (CH),
70.28 (CH), 67.86 (CH), 62.18 (CH2), 61.62 (CH2), 20.87
(CH3), 20.77 (CH3), 20.73 (CH3), 20.61 (4CH3); IR (neat):
n=3462, 3369, 3224, 3010, 2588, 2319, 2215, 2143, 1755,
1741, 1367, 1230, 1213, 1036 cmÀ1; HR-MS (ESI): m/z=
777.2036, calculated for C34H42NaO17S: 777.2035.
(2R,3R,4S,5R,6S)-3,4,5-Tris(benzyloxy)-2-[(benzyloxy)-
methyl]-6-{[(E)-styryl]thio}tetrahydro-2H-pyran
(3r):
yield: 120 mg (73%); Rf =0.62 (cyclohexane:AcOEt, 8:2);
white-yellow solid; mp 86–888C; [a]2D4: +80.0 (c 1.0, CHCl3);
1H NMR (300 MHz, acetone): d=7.45–7.21 (m, 25H), 7.14
8
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Stereoselective Palladium-Catalyzed Alkenylation and Alkynylation of Thioglycosides
(2R,3S,4S,5R,6S)-2-(Hydroxymethyl)-6-{[1-(3,4,5-trime-
thoxyphenyl)vinyl]thio}tetrahydro-2H-pyran-3,4,5-triol
(3u): yield: 66 mg (65%); Rf =0.33 (DCM:MeOH, 85:15);
white-yellow solid; mp 86–888C; [a]2D4: À70.0 (c 1.0,
(CH), 127.08 (CH), 126.73 (CH), 120.01 (C), 97.60 (C),
84.65 (CH), 76.66 (CH), 74.01 (CH), 73.08 (C), 69.98 (CH),
67.99 (CH), 62.08 (CH2), 20.84 (CH3), 20.81 (CH3), 20.73
(CH3), 20.70 (CH3); IR (neat): n=3284, 3207, 2370, 2163,
1954, 1757, 1745, 1711, 1365, 1210, 1060 cmÀ1; HR-MS
(ESI): m/z=537.1183, calculated for C26H26NaO9S:
537.1195.
1
MeOH); H NMR (300 MHz, MeOD): d=6.91 (s, 2H), 5.55
(s, 1H), 5.53 (s, 1H), 4.49 (d, J=9.2 Hz, 1H), 3.86 (s, 6H),
3.83 (d, J=2.4 Hz, 1H), 3.79 (d, J=2.3 Hz, 1H), 3.77 (s,
3H), 3.67–3.58 (m, 2H), 3.33 (s, 1H), 3.20–3.07 (m, 1H);
13C NMR (75 MHz, MeOD): d=154.25 (C), 144.62 (C),
139.15 (C), 136.74 (C), 115.21 (CH2), 106.20 (2CH), 87.67
(CH), 81.97 (CH), 79.75 (CH), 74.06 (CH), 71.29 (CH),
62.74 (CH2), 61.14 (CH3), 56.69 (2CH3); IR (neat): n=3438,
3386, 3356, 3301, 3252, 2526, 2253, 2159, 2025, 1946, 1756,
1217, 1037 cmÀ1; HR-MS (ESI): m/z=411.1076, calculated
for C17H24NaO8S: 411.1084.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-{[(4-cyanophe-
nyl)ethynyl]thio}tetrahydro-2H-pyran-3,4,5-triyl triacetate
(5c): yield: 113 mg (93%); Rf =0.41 (cyclohexane:AcOEt, 6:
4); white-yellow solid; mp 87–898C; [a]2D4: À71.0 (c 1.0,
1
CHCl3); H NMR (300 MHz, CDCl3): d=7.61 (d, J=8.6 Hz,
2H), 7.55 (d, J=8.6 Hz, 2H), 5.38–5.23 (m, 2H), 5.14 (t, J=
9.6 Hz, 1H), 4.62 (d, J=9.4 Hz, 1H), 4.26 (dd, J=12.5,
4.9 Hz, 1H), 4.17 (dd, J=12.5, 2.4 Hz, 1H), 3.80 (ddd, J=
10.0, 4.9, 2.4 Hz, 1H), 2.08 (s, 3H), 2.05 (s, 3H), 2.03 (s,
3H), 2.02 (s, 3H); 13C NMR (75 MHz, CDCl3): d=170.64
(C=O), 170.25 (C=O), 169.48 (C=O), 169.12 (C=O), 132.19
(4CH), 127.56 (C), 118.51 (C), 112.02 (C), 95.96 (C), 84.23
(CH), 78.35 (CN), 76.84 (CH), 73.94 (CH), 69.83 (CH),
67.95 (CH), 62.09 (CH2), 20.82 (CH3), 20.68 (3CH3); IR
(neat): n=3489, 3428, 2360, 2173, 1756, 1488, 1366, 1212,
1090 cmÀ1; HR-MS (ESI): m/z=512.0988, calculated for
C23H23NNaO9S: 512.0991.
(2R,3R,4S,5R,6S)-2-(Hydroxymethyl)-6-{[1-(3,4,5-tri-
methoxyphenyl)vinyl]thio}tetrahydro-2H-pyran-3,4,5-triol
(3v):yield: 59 mg (60%); Rf =0.33 (DCM:MeOH, 85:15);
white-yellow solid; mp 90–928C; [a]2D4: À107.0 (c 1.0,
1
MeOH); H NMR (300 MHz, MeOD): d=6.92 (s, 2H), 5.54
(s, 2H), 4.46 (d, J=9.8 Hz, 1H), 3.87 (m, 1H), 3.86 (s, 6H),
3.77 (s, 3H), 3.71–3.59 (m, 4H), 3.48–3.38 (m, 2H);
13C NMR (75 MHz, MeOD): d=154.24 (C), 144.84 (C),
143.65 (C), 136.78 (C), 115.02 (CH2), 106.13 (CH), 88.23
(CH), 80.54 (CH), 76.34 (CH), 71.16 (CH), 70.33 (CH),
62.46 (CH2), 61.13 (CH3), 56.65 (2CH3); IR (neat): n=3476,
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-{[(E)-4-phenyl-
but-3-en-1-yn-1-yl]thio}tetrahydro-2H-pyran-3,4,5-triyl
triacetate (5d): yield: 61 mg (50%); Rf =0.58 (cyclohex-
3342, 3315, 2431, 2357, 2192, 2106, 1991, 1576, 1323 cmÀ1
;
AHCTUNGTRENNUNG
ane:AcOEt, 5: 5); black oil; [a]2D4: +54.0 (c 1.0, CHCl3);
HR-MS (ESI): m/z=411.1076, calculated for C17H24NaO8S:
411.1084.
1H NMR (300 MHz, CDCl3). d=7.46–7.27 (m, 5H), 7.01 (d,
J=16.2 Hz, 1H), 6.26 (d, J=16.2 Hz, 1H), 5.33–5.20 (m,
2H), 5.15 (ddd, J=9.6, 6.8, 2.8 Hz, 1H), 4.59 (dd, J=7.0,
2.6 Hz, 1H), 4.27 (dd, J=12.5, 4.8 Hz, 1H), 4.18 (dd, J=
12.4, 2.4 Hz, 1H), 3.79 (ddd, J=9.9, 4.8, 2.4 Hz, 1H), 2.09 (s,
3H), 2.08 (s, 3H), 2.03 (s, 3H), 2.02 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=170.76 (C=O), 170.32 (C=O), 169.47
(C=O), 169.17 (C=O), 142.59 (CH), 136.11 (C), 129.02
(CH), 128.87 (2CH), 126.54 (2CH), 107.73 (CH), 96.85 (C),
84.70 (CH), 76.66 (CH), 74.78 (C), 74.01 (CH), 70.05 (CH),
68.06 (CH), 62.13 (CH2), 20.87 (CH3), 20.77 (CH3), 20.70
(2CH3); IR (neat): n=3479, 3443, 3327, 3300, 3222, 2867,
2372, 2316, 2135, 2021, 1967, 1756, cmÀ1; HR-MS (ESI):
m/z=513.1180, calculated for C24H26NaO9S: 513.1190.
Analytical Data for Alkynylthioglycosides 5a–e and
Product 7
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-{[(4-methoxyphe-
nyl)ethynyl]thio}tetrahydro-2H-pyran-3,4,5-triyl triacetate
(5a): yield: 56 mg (45%); (Rf =0.31 cyclohexane:AcOEt, 7:
3); white-yellow oil; [a]2D4: À43.0 (c 1.0, CHCl3); 1H NMR
(300 MHz, CDCl3): d=7.45 (d, J=8.9 Hz, 2H), 6.85 (d, J=
8.9 Hz, 2H), 5.29 (td, J=17.0, 9.2 Hz, 2H), 5.17–5.09 (m,
1H), 4.59 (d, J=9.4 Hz, 1H), 4.26 (dd, J=12.5, 4.8 Hz, 1H),
4.18 (dd, J=12.5, 2.5 Hz, 1H), 3.82 (s, 3H), 3.80–3.73 (m,
1H), 2.10 (s, 3H), 2.06 (s, 3H), 2.03 (s, 3H), 2.01 (s, 3H);
13C NMR (75 MHz, CDCl3): d=170.78 (C=O), 170.34 (C=
O), 169.46 (C=O), 169.15 (C=O), 160.39 (C), 134.22 (2CH),
114.87 (C), 114.13 (2CH), 97.29 (C), 84.71 (CH), 76.65
(CH), 74.11 (CH), 70.93 (C), 69.96 (CH), 68.08 (CH), 62.16
(CH2), 55.47 (CH3), 20.85 (CH3), 20.82 (CH3), 20.71 (2CH3);
IR (neat): n=3422, 3337, 3215, 3106, 2483, 2263, 2030, 1987,
1758, 1509, 1251 cmÀ1; HR-MS (ESI): m/z=517.1136, calcu-
lated for C23H26NaO10S: 517.1139.
(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-
{[(2R,3R,5R,6S)-4,5-diacetoxy-2-(acetoxymethyl)-6-{[(4-
cyanophenyl)ethynyl]thio}tetrahydro-2H-pyran-3-yl]oxy}te-
trahydro-2H-pyran-3,4,5-triyl triacetate (5e): yield: 126 mg
(65%); Rf =0.30 (cyclohexane:AcOEt, 6:4); white-yellow
solid; mp 74–768C; [a]2D4: À20.0 (c 1.0, CHCl3); 1H NMR
(300 MHz, CDCl3): d=7.59 (d, J=8.6 Hz, 2H), 7.52 (d, J=
8.5 Hz, 2H), 5.27–5.17 (m, 2H), 5.15–5.01 (m, 2H), 4.95–
4.82 (m, 1H), 4.64–4.54 (m, 1H), 4.50 (d, J=8.1 Hz, 2H),
4.36 (dd, J=12.5, 4.1 Hz, 1H), 4.10 (dd, J=12.2, 5.3 Hz,
1H), 4.02 (dd, J=12.4, 2.0 Hz, 1H), 3.92–3.75 (m, 1H),
3.75–3.58 (m, 2H), 2.06 (s, 3H), 2.06 (s, 3H), 2.05 (s, 3H),
2.01 (s, 3H), 2.00 (s, 3H), 1.98 (s, 3H), 1.96 (s, 3H);
13C NMR (75 MHz, CDCl3): d=170.49 (C=O), 170.28 (C=
O), 170.24 (C=O), 169.79 (C=O), 169.35 (2C=O), 169.12
(C=O), 132.14 (4CH), 127.59 (C), 118.42 (C), 111.97 (C),
100.91 (CH), 95.57 (C), 84.21 (CH), 78.74 (CN), 77.68 (CH),
76.07 (CH), 73.70 (CH), 72.94 (CH), 72.07 (CH), 71.68
(CH), 70.01 (CH), 67.87 (CH), 62.06 (CH2), 61.64 (CH2),
20.88 (CH3), 20.71 (2CH3), 20.60 (4CH3); IR (neat): n=
(2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-((naphthalen-1-
ylethynyl)thio)tetrahydro-2H-pyran-3,4,5-triyl
triacetate
(5b): yield: 87 mg (68%); Rf =0.32 (cyclohexane:AcOEt, 7:
1
3); white-yellow oil; [a]2D4: +47.0 (c 1.0, CHCl3); H NMR
(300 MHz, CDCl3): d=8.02 (s, 1H), 7.85–7.73 (m, 3H), 7.51
(m, 3H), 5.33 (dt, J=22.5, 9.2 Hz, 2H), 5.16 (t, J=9.5 Hz,
1H), 4.66 (d, J=9.4 Hz, 1H), 4.28 (dd, J=12.5, 4.8 Hz, 1H),
4.20 (dd, J=12.5, 2.2 Hz, 1H), 3.81 (ddd, J=9.9, 4.7, 2.3 Hz,
1H), 2.12 (s, 3H), 2.05 (s, 3H), 2.04 (s, 3H), 2.03 (s, 3H);
13C NMR (75 MHz, CDCl3): d=170.79 (C=O), 170.35 (C=
O), 169.47 (C=O), 169.18 (C=O), 133.17 (C), 132.96 (C),
132.32 (CH), 128.59 (CH), 128.15 (CH), 128.01 (CH), 127.89
Adv. Synth. Catal. 0000, 000, 0 – 0
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Etienne Brachet et al.
FULL PAPERS
3411, 3338, 3231, 2363, 2227, 2076, 2030, 1970, 1758, 1741,
1603, 1366, 1228, 1168, 1035 cmÀ1; HR-MS (ESI): m/z=
800.1815, calculated for C35H39NNaO17S: 800.1831.
[3] M. Adinolfi, M. d’Ischia, A. Iadonisi, L. Leone, A. Pez-
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(2R,3R,4S,5R,6S)-2-(Acetoxymethyl)-6-{[(Z)-1-(4-ace-
toxyphenyl)-3-ethoxy-3-oxoprop-1-en-2-yl]thio}tetrahydro-
2H-pyran-3,4,5-triyl triacetate (7): yield: 96 mg (65%);
Rf =0.42 (cyclohexane:AcOEt, 5: 5); white-yellow solid; mp
1
88–908C; [a]2D4: +59.0 (c 1.0, CHCl3); H NMR (300 MHz,
CDCl3): d=8.01 (s, 1H), 7.85 (d, J=8.6 Hz, 2H), 7.12 (d,
J=8.6 Hz, 2H), 5.24–5.13 (m, 1H), 5.06 (t, J=9.6 Hz, 2H),
4.90 (d, J=9.9 Hz, 1H), 4.33 (q, J=7.1 Hz, 2H), 4.19 (dd,
J=12.4, 5.0 Hz, 1H), 4.01 (dd, J=12.3, 2.2 Hz, 1H), 3.61
(ddd, J=7.4, 4.7, 2.2 Hz, 1H), 2.30 (s, 3H), 2.01 (s, 3H),
2.00 (s, 3H), 1.98 (s, 3H), 1.94 (s, 3H), 1.39 (t, J=7.1 Hz,
3H); 13C NMR (75 MHz, CDCl3): d=170.70 (C=O), 170.29
(C=O), 169.53 (C=O), 169.47 (C=O), 169.13 (C=O), 165.91
(C=O), 151.91 (C), 146.29 (CH), 132.58 (2CH), 131.77 (C),
122.77 (C), 121.61 (2CH), 84.47 (CH), 76.02 (CH), 74.07
(CH), 71.03 (CH), 68.36 (CH), 62.17 (CH2), 62.09 (CH2),
21.27 (CH3), 20.68 (4CH3), 14.46 (CH3); IR (neat): n=3428,
3247, 3144, 2359, 2237, 2168, 2017, 2001, 1754, 1712, 1601,
1505, 1368, 1217, 1194, 1037 cmÀ1; HR-MS (ESI): m/z=
619.1455, calculated for C27H32NaO13S: 619.1456.
Acknowledgements
The CNRS is gratefully acknowledged for financial support
of this research and Ministꢀre (MENRT) for a doctoral fel-
lowship to EB. Our laboratory BioCIS-UMR 8076 is
a member of the Laboratory of Excellence LERMIT sup-
ported by a grant from ANR (ANR-10-LABX-33).
[8] E. Brachet, J.-B. Brion, S. Messaoudi, M. Alami, Adv.
Synth. Catal. 2013, 355, 477–490.
[9] Selected representative examples for the Pd-catalyzed
À
C S cross-coupling reaction see: a) M. Murata, S. L.
Buchwald, Tetrahedron 2004, 60, 7397–7403; b) T. Itoh,
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[10] As we reported in our previous study (see ref.[6]), the
use of a 1:1 PdACHTNUTRGNEUNG(OAc)2/Xantphos ratio decreases signifi-
cantly the yield of the coupling product 3a (61% yield).
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Stereoselective Palladium-Catalyzed Alkenylation and
Alkynylation of Thioglycosides
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Etienne Brachet, Jean-Daniel Brion, Mouad Alami,*
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