One-pot synthesis of aryl biaryl sulfones

Article abstract of DOI:10.1016/j.tetlet.2013.10.067

Synthesis of aryl biaryl sulfones 3 with good yields is described. The one-pot efficient synthetic route is carried by the NaH-mediated tandem [C3 + C3] annulations of cinnamaldehydes 1 and propargylic sulfones 2 under the boiling THF conditions.

Full text of DOI:10.1016/j.tetlet.2013.10.067

Tetrahedron Letters 54 (2013) 6971–6974
Contents lists available at ScienceDirect
Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
One-pot synthesis of aryl biaryl sulfones
⇑
Meng-Yang Chang , Ming-Hao Wu, Chieh-Kai Chan, Shin-Ying Lin
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan
a r t i c l e i n f o
a b s t r a c t
Article history:
Synthesis of aryl biaryl sulfones 3 with good yields is described. The one-pot efficient synthetic route is
carried by the NaH-mediated tandem [C3+C3] annulations of cinnamaldehydes 1 and propargylic
sulfones 2 under the boiling THF conditions.
Received 11 July 2013
Revised 9 October 2013
Accepted 15 October 2013
Available online 23 October 2013
Ó 2013 Elsevier Ltd. All rights reserved.
Keywords:
One-pot synthesis
Aryl biaryl sulfones
Cinnamaldehydes
Propargylic sulfones
Introduction
treatment of commercially available cinnamaldehydes 1 with
substituted propargylic sulfones 2 under the boiling THF conditions.
Construction of diaryl sulfones with different functional groups
has drawn much attention since they constitute useful building
blocks in organic and medicinal chemistry.1 Their biological activ-
ities and chemical properties have emerged as key targets since the
sulfonyl substituent has been used as the main constituent of
many drugs, such as nonsteroidal anti-inflammatory drugs
(DuP-697, SC-58125, MK 966),2 selective COX-2 inhibitors
(Vioxx),3 useful prostaglandin D2 antagonist (MK-0524),4 and other
potential pharmaceutical molecules.5 There are a number of
processes available to generate the structural skeleton of diaryl
sulfones,6–10 but they are generally synthesized by the oxidation
of the resulting aryl sulfides,6a the electrophilic aromatic substitu-
tion of arenes with arenesulfonic acids in the presence of strong
acids7 or with arenesulfonyl halides,8 the reaction of carbon elec-
trophiles with sulfinate salts,9 and the reaction of organometallic
compounds with sulfinate or sulfonate ester.10
Results and discussion
As shown in Scheme 1, aryl biaryl sulfones 3 can be prepared via
NaH-mediated one-pot annulation of cinnamaldehydes 1 with
propargylic sulfones 2 in good yields. Skeleton 2 is synthesized
using nucleophilic substitution of propargylic bromides with sulfi-
nic sodium salts with 45–85% yields. For investigating one-pot
reaction conditions, we found that treatment of model compound
1a (X = H) with compound 2a (Y = R = Me) provided compound
3a as a sole isomer in a 75% yield in the presence of NaH (3.0 equiv)
in boiling THF, which was better than NaNH2 (70%) or DBU (68%).
This is an efficient synthetic route to achieve the structural skele-
ton of aryl biaryl sulfones (sulfonyl biaryls), and its sulfonyl group
can also be introduced with a specific site-selectivity during the
annulation procedure.
Although a number of diaryl sulfones and their derivatives with
this specific substitution pattern have been developed by almost all
multi-step reactions, new methods for their novel and efficient
preparation are needed. In continuation of our previous investiga-
tions on one-pot synthesis of monocyclic cyclohexanes,11a tricyclic
benzo[g]indazoles and tetrahydrocyclobuta[a]naphthalenes,11b,c
and polycyclic azahomoisotwistanes and tetrahydrobenzo[j]fluo-
ranthen-12-ones,11d,e a transition-metal free and one-pot expedi-
tious cascade methodology12,13 for establishing the framework of
aryl biaryl sulfones 3 was developed via the NaH-mediated
With the result in hand, one-pot preparation of substituted
skeleton 3 was further examined. By changing X, Y, and R groups
Y
R
O
Y
O
S
3
4
1
R
S
O
2
1
NaH, THF
reflux
O
+
X
X
O
3
H
⇑
Corresponding author. Tel.: +886 7 3121101x2220.
E-mail address: mychang@kmu.edu.tw (M.-Y. Chang).
Scheme 1. The synthetic route of aryl biaryl sulfones 3.
0040-4039/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetlet.2013.10.067

6972
M.-Y. Chang et al. / Tetrahedron Letters 54 (2013) 6971–6974
Table 1
Synthesis of aryl biaryl sulfones 3a
Y
O
S
Me
X
NaH (3.0 equiv)
THF, reflux, 3 h
R
Y
O
S
O
O
+
H
O
X
1
2
3
Entry
1
cinnamaldehydes1
sulfones 2
product 3, yield (%)
Entry
14
cinnamaldehydes1
sulfones 2
product 3, yield (%)
F
Me
O
O
S
Me
S
Me
O
O
H
Me
F
O
O
Me
Me
H
O
O
S
S
O
MeO
MeO
1a
2a
3a, 75
1b
2dO
3n, 85
F
Me
O
Me
S
O
O
H
O
Me
S
O
Me
F
O
2
3
15
16
Me
Me
H
Me
N
Me
Me
N
Me
O
S
O
S
MeO
O
MeO
1b
2a
3b, 78
1c
2dO
3o, 74
Me
F
O
Me
S
O
O
H
O
Me
S
O
Me
F
O
Me
Me
Me
N
Me
Me
H
O
S
O
S
N
O
Me
F
F
1c
2a
3c, 82
1d
2dO
3p, 67
Me
Br
O
S
O
O
S
Me
Me
O
O
Me
Br
O
Me
Me
Me
4
5
17
18
H
H
O
S
O
S
F
O
F
MeO
O
MeO
MeO
1d
2a
3d, 63
1b
2e
3q, 64
Et
O
O
Me
S
O
Me
Me
S
O
O
H
Et
O
Me
H
O
S
O
S
Me
O
MeO
O
1a
2b
3e, 74
1b
2f
3r, 72
Me
Me
Et
O
S
O
S
O
Me
Me
Me
Me
Me
Me
O
O
Et
O
6
7
19
20
Me
Me
Me
Me
H
H
O
S
O
S
MeO
O
MeO
MeO
O
MeO
1b
2b
3f, 75
1b
2g
3s, 75
Et
O
S
Me
O
S
O
O
H
O
O
Et
Me
Me
N
Me
Me
H
O
S
O
N
S
O
Me
MeO
O
MeO
1c
2b
3g, 82
1b
2h
3t, 76
Me
Et
Me
Me
O
S
O
O
S
O
Me
Me
Me
O
O
Et
8
9
21
22
23
Me
Me
H
H
O
S
O
S
F
O
F
MeO
O
MeO
1d
2b
3h, 86
1b
2i
3u, 81
Me
OMe
O
O
S
O
Me
S
Me
O
H
O
H
O
OMe
Me
Me
Me
O
O
S
S
NO
NO
O
O
1a
2c
3i, 80
1e2
2a
32v, --b
Me
OMe
Me
O
O
S
O
Me
Me
S
O
O
H
Me
OMe
O
Me
10
Me
H
O
O
S
Me
S
MeO
O
MeO
O
1b
2c
3j, 74
1a
2j
3w / 82
OMe
Me
O
Me
Me
S
O
O
S
O
H
Me
Me
O
Me
OMe
O
11
12
13
24
25
26
Me
Me
N
Me
Me
H
O
O
Me
N
Me
S
S
O
MeO
O
MeO
1c
2c
3k, 78
1b
2j
3x / 80
Me
Me
OMe
O
S
O
S
O
O
H
Me
Me
Me
O
Me
O
OMe
Me
H
Me
N
Me
Me
N
Me
O
O
Me
S
S
F
O
F
O
1d
2c
3l, 76
1c
2j
3y / 76
Me
Me
F
O
S
O
O
S
O
Me
Me
Me
O
Me
O
H
F
Me
H
O
S
2dO
O
Me
S
F
O
F
1a
3m, 82
1d
2j
3z / 76
a
For the best one-pot reaction conditions: (i) substituted cinnamaldehydes 1 (1.0 mmol), propargylic sulfones 2 (1.0 mmol), NaH (60% in oil, 120 mg, 3.0 mmol), THF
(15 mL), reflux, 3 h.
bUnknown mixture was obtained.

M.-Y. Chang et al. / Tetrahedron Letters 54 (2013) 6971–6974
6973
in the aryl substituent of skeletons 1 and 2, the diversified aryl
O
Me
S
2
biaryl sulfones (3-alky-4-aryl-1-arylsulfonyl benzenes) 3a–z were
isolated in good yields by one-pot domino methodology with the
expected compound 3v; they are summarized in Table 1.14 The
o-nitrophenyl substituent of compound 1e should inhibit the for-
mation of compound 3v. The skeletons 3 were confirmed through
spectral analysis, including 1H and 13C NMR and HRMS spectra. The
structures of compounds 3b, 3j, 3l, and 3w were determined by
single-crystal X-ray crystallography.15
Compared with the isolated yields of products 3, it was found
that there was no obvious interference from different kinds of sub-
stituents (e.g., electron-withdrawing oxygen-containing groups;
electron-donating fluoro-containing groups) in the product yields
using the one-pot domino [C3+C3] reaction route. This is a novel,
high-yield, and one-pot cascade route to the framework of func-
tionalized sulfonyl biphenyls 3. As shown in Scheme 2, a plausible
explanation for preparing compound 3a should be that intermedi-
MeSO Na, dioxane/H O
2
2
O
3
O
Me
reflux, 3 h
S
O
Br
2k (45%)
MeSO Na
MeSO Na
2
2
O
S
O
S
Me
Me
C
O
H
O
Scheme 3. Synthesis of compound 2k.
Y
Y
NaH, THF
reflux
Ph
O
complex
mixture
ate A of sodium
a-sulfonyl carbanion was first generated via a
O
O
+
S
S
H
NaH-mediated deprotonation of compound 2a in refluxing THF.
Under the thermodynamic condition, intermediate C, with a
(E,E)-conjugated configuration, was afforded from 1,2-addition of
intermediate A followed by sequential dehydration of intermediate
B. If the dehydration occurred from antiperiplanar orientation be-
tween hydrogen group and hydroxyl group, the ratio of (E,E) and
(E,Z)-isomers would be determined by threo/erythro intermediate
of b-hydroxyl sulfone. Under our one-pot condition, no isolation of
(Z,E)-isomer was observed. It should be easy to form due to a stron-
ger repulsion with steric hindrance than intermediate C had.
According to Ogura reports,6b the similar isomer with (E)-orienta-
tion had been formed as the sole product via the n-BuLi-mediated
O
O
Y
S
1a
2l, Y = Et
2m, Y = OMe
Y
O
O
O
S
O
5
No detected
Scheme 4. Reaction of compound 2l or 2m with compound 1a.
dehydration of
a-sulfonyl carbanion and cinnamaldehyde. There-
fore, we believed that the dehydration should occur from the pla-
nar sp2-like sulfonyl carbanion. Next, the formation of compound
3a was observed via the stepwise ring-closure of intermediate C
followed by the sequential hydrogen migration of intermediate D
(an aromatization process).
To explore other biphenyls with sulfonyl groups, compounds 2l
and 2m with two sulfonyl groups and one alkyne motif were fur-
ther examined to establish the skeleton of bis-sulfonyl biphenyls
5. When the methyl group of 2-butynyl arylsulfone was changed
to methylsulfonyl substituent, one-pot reaction of compound 2l
or 2m with compound 1a afforded a complex mixture under the
above mentioned conditions (Scheme 4).
To further evaluate the synthetic scope of skeleton 2, the termi-
nal alkyl group (R = Me or Et) was changed to phenyl group (R = Ph)
and the arylsulfonyl group (Ar) was changed to methylsulfonyl
group (Me), as shown in Scheme 3. Especially, treatment of
1-bromo-3-phenyl-2-propyne with methylsulfinic sodium salt
(MeSO2Na) afforded compound 2k in 45% yield. This is a facile route
for synthesizing 2,3-bis-sulfonylpropenes.16 From the experimental
results, the reaction pathway included a double nucleophilic addi-
tion and the formation of sulfonyl allene intermediate. The struc-
ture of compound 2k was determined by single-crystal X-ray
crystallography.15 For the shown yields in Table 1, different aryl
or aliphatic functionalities of these substrates provided the skele-
ton of biphenyl with good yields and excellent regioselectivity.
Conclusion
In summary, we have successfully presented a synthetic route
for the synthesis of sulfonyl biphenyls 3 via NaH-mediated domino
annulations of cinnamaldehydes 1 with propargylic sulfones 2 in
refluxing THF. The structures of key products were confirmed by
X-ray crystal analysis. The one-pot transition metal-free synthetic
approach begins with simple starting materials and reagents, and
provides a potential methodology for the synthetic research and
biological activities of sulfonyl biphenyls. Further studies regarding
one-pot cascade synthesis of multi-functionalized carbocycles will
be conducted and published in due course.
addition
Me
2a
O
Me
O
Tol
Tol
Me
Ph
O
S
S
Tol
Acknowledgment
S
NaH
THF
O
A
O
O
+
The authors would like to thank the National Science Council of
the Republic of China for its financial support (NSC 102-2113-M-
037-005-MY2).
O
Ph
O
Ph
O
1a
B
H
H
dehydration
ring-closure
O
hydrogen migration
Supplementary data
Me
O
S
O
Tol
Tol
Tol
Me
S
Me
S
Supplementary data (experimental procedures, characteriza-
tion data and scanned photocopies of 1H and 13C NMR of skeletons
2–3, and crystallographic data of compounds 3b, 3j, 3l and 3w)
associated with this article can be found, in the online version, at
http://dx.doi.org/10.1016/j.tetlet.2013.10.067.
O
O
O
Ph
H
Ph
H
Ph
H
H
(E,E)-C
3a
D
Scheme 2. A possible mechanism to compound 3a.

6974
M.-Y. Chang et al. / Tetrahedron Letters 54 (2013) 6971–6974
Ma, D. J. Org. Chem. 2005, 70, 2696; (d) Yuan, G.; Zheng, J.; Gao, X.; Li, X.; Huang,
References and notes
L.; Chen, H.; Jiang, H. Chem. Commun. 2012, 7513.
11. (a) Chang, M.-Y.; Wu, M.-H. Tetrahedron 2012, 68, 9616; (b) Chang, M.-Y.; Tai,
H.-Y.; Chen, Y.-L.; Hsu, R.-T. Tetrahedron 2012, 68, 7941; (c) Chang, M.-Y.; Wu,
M.-H.; Chen, Y.-L. Org. Lett. 2013, 15, 2822; (d) Chang, M.-Y.; Wu, M.-H.; Tai, H.-
Y. Org. Lett. 2012, 14, 3936; (e) Chang, M.-Y.; Lee, T.-W.; Wu, M.-H. Org. Lett.
2012, 14, 2198; (f) Chang, M.-Y.; Chan, C.-K.; Wu, M.-H. Tetrahedron 2013, 69,
7916; (g) Chang, M.-Y.; Chan, C.-K.; Lin, S.-Y.; Wu, M.-H. Tetrahedron 2013, 69,
9616.
12. For reviews of Suzuki–Miyaura cross-coupling reactions, see: (a) Bringmann,
G.; Walter, R.; Weirich, R. Angew. Chem., Int. Ed. Engl. 1990, 29, 977; (b)
Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457; (c) Herrmann, W. A. Angew.
Chem., Int. Ed. 2002, 41, 1290; (d) Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed.
2002, 41, 4176.
13. (a) Hegedus, L. S. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley:
Chichester, UK, 2002; p 1123; (b)Handbook of Organopalladium Chemistry for
Organic Synthesis; Negishi, E., Ed.; Wiley-Interscience: New York, NY, 2002; (c)
Diederich, F.; Stang, P. J. Metal-Catalyzed Cross-Coupling Reactions; Wiley-VCH:
Weinheim, 1998; (d) Miyaura, N. Cross-Coupling Reaction; Springer: Berlin,
2002; (e) de Meijere, A.; Diederich, F. Metal-Catalyzed Cross-Coupling Reactions;
Wiley-VCH: Weinheim, 2004.
1. For some examples, see: (a) Yoshihara, S.; Tatsumi, K. Drug Metab. Dispos. 1990,
18, 876; (b) Sato, H.; Clark, D. P. Microbios 1995, 83, 145; (c) Jones, T. R.;
Webber, S. E.; Varney, M. D.; Reddy, M. R.; Lewis, K. K.; Kathardekar, V.;
Mazdiyasni, H.; Deal, J.; Nguyen, D.; Welsh, K. M.; Webber, S.; Johnson, A.;
Matthews, D. A.; Smith, W. W.; Janson, C. A.; Bacquet, R. J.; Howland, E. F.;
Booth, C. L. J.; Ward, R. W.; Herrmann, S. M.; White, J.; Bartlett, C. A.; Morse, C.
A. J. Med. Chem. 1997, 40, 677; (d) Caron, G.; Gaillard, P.; Carrupt, P. A.; Testa, B.
Helv. Chim. Acta 1997, 80, 449; (e) Seydel, J. K.; Burger, H.; Saxena, A. K.;
Coleman, M. D.; Smith, S. N.; Perris, A. D. Quant. Struct.-Act. Relat. 1999, 18, 43;
(f) Dinsmore, C. J.; Williams, T. M.; O’Neill, T. J.; Liu, D.; Rands, E.; Culberson, J.
C.; Lobell, R. B.; Koblan, K. S.; Kohl, N. E.; Gibbs, J. B.; Oliff, A. I.; Graham, S. L.;
Hartman, G. D. Bioorg. Med. Chem. Lett. 1999, 9, 3301; (g) Sun, Z.-Y.; Botros, E.;
Su, A.-D.; Kim, Y.; Wang, E.; Baturay, N. Z.; Kwon, C.-H. J. Med. Chem. 2000, 43,
4160; (h) Faucher, A.-M.; White, P. W.; Brochu, C.; Grand-Maitre, C.; Rancourt,
J.; Fazal, G. J. Med. Chem. 2004, 47, 18.
2. (a) Miyamae, T.; Hashizume, H.; Ogawa, T.; Okayama, T.; Nukui, E.; Oshima, K.;
Morikawa, T.; Hagiwara, M. Arzneim. Forsch. 1997, 47, 13; (b) Ohkanda, J.;
Lockman, J. W.; Kothare, M. A.; Qian, Y.; Blaskovich, M. A.; Sebti, S. M.;
Hamilton, A. D. J. Med. Chem. 2002, 45, 177; (c) Chakraborty, S.; Sengupta, C.;
Roy, K. Bioorg. Med. Chem. Lett. 2004, 14, 4665; (d) Pinto, D. J. P.; Batt, D. G.;
Pitts, W. J.; Petraitis, J. J.; Orwat, M. J.; Wang, S.; Jetter, J. W.; Sherk, S. R.;
Houghton, G. C.; Copeland, R. A.; Covington, M. B.; Trzaskos, J. M.; Magolda, R. L.
Bioorg. Med. Chem. Lett. 1999, 9, 919.
14. A representative synthetic procedure of skeleton 3 is as follows: Sodium hydride
(NaH, 60% in oil, 120 mg, 3.0 mmol) was added to a solution of propargylic
sulfones
2 (1.0 mmol) in THF (8 mL). A solution of cinnamaldehydes 1
(1.0 mmol) in the THF (7 mL) was added to the reaction mixture at rt. The
reaction mixture was stirred at reflux for 3 h. The reaction mixture was cooled
to rt. Water (1 mL) was added to the reaction mixture at 0 °C. The solvent was
concentrated under reduced pressure. The residue was diluted with water
(10 mL) and the mixture was extracted with EtOAc (3 Â 20 mL). The combined
organic layers were washed with brine, dried, filtered, and evaporated to afford
crude product. Purification on silica gel (hexanes/EtOAc = 10/1–6/1) afforded
skeleton 3. For 3j: Yield = 74% (272 mg); mp = 162–163 °C (recrystallized from
hexanes and EtOAc); HRMS (ESI, M++1) calcd for C21H21O4S 369.1161, found
3. Prasit, P.; Wang, Z.; Brideau, C.; Chan, C.-C.; Charleson, S.; Cromlish, W.; Ethier,
D.; Evans, J. F.; Ford-Hutchinson, A. W.; Gauthier, J. Y.; Gordon, R.; Guay, J.;
Gresser, M.; Kargman, S.; Kennedy, B.; Leblanc, Y.; Leger, S.; Mancini, J.; O’Neill,
G. P.; Ouellet, M.; Percival, M. D.; Perrier, H.; Riendeau, D.; Rodger, I.; Tagari, P.;
Therien, M.; Vickers, P.; Wong, E.; Xu, L.-J.; Young, R. N.; Zamboni, R. Bioorg.
Med. Chem. Lett. 1999, 9, 1773.
4. Sturino, C. F.; O’Neill, G.; Lachance, N.; Boyd, M.; Berthelette, C.; Labelle, M.; Li,
L.; Roy, B.; Scheigetz, J.; Tsou, N.; Aubin, Y.; Bateman, K. P.; Chauret, N.; Day, S.
H.; Levesque, J.-F.; Seto, C.; Silva, J. H.; Trimble, L. A.; Carriere, M.-C.; Denis, D.;
Greig, G.; Kargman, S.; Lamontagne, S.; Mathieu, M.-C.; Sawyer, N.; Slipetz, D.;
Abraham, W. M.; Jones, T.; McAuliffe, M.; Piechuta, H.; Nicoll-Griffith, D. A.;
Wang, Z.; Zamboni, R.; Young, R. N.; Metters, K. M. J. Med. Chem. 2007, 50, 794.
5. (a) McMahon, J. B.; Gulakowsky, R. J.; Weislow, O. S.; Schultz, R. J.; Narayanan,
V. L.; Clanton, D. J.; Pedemonte, R.; Wassmundt, F. W.; Buckheit, R. W., Jr.;
Decker, W. D.; White, E. L.; Bader, J. P.; Boyd, M. R. Antimicrob. Agents
Chemother. 1993, 37, 754; (b) Williams, T. M.; Ciccarone, T. M.; MacTough, S. C.;
Rooney, C. S.; Balani, S. K.; Condra, J. H.; Emini, E. A.; Goldman, M. E.; Greenlee,
W. J.; Kauffman, L. R.; O’Bnen, J. A.; Sardana, V. V.; Schleif, W. A.; Theoharides, A.
D.; Anderson, P. S. J. Med. Chem. 1993, 36, 1291; (c) Neamati, N.; Mazumder, A.;
Zhao, H.; Sunder, S.; Burke, T. R., Jr.; Schultz, R. J.; Pommier, Y. Antimicrob.
Agents Chemother. 1997, 41, 385.
369.1165; 1H NMR (400 MHz, CDCl3):
d 7.91 (d, J = 9.2 Hz, 2H), 7.79 (d,
J = 1.6 Hz, 1H), 7.74 (dd, J = 1.6, 8.0 Hz, 1H), 7.30 (d, J = 8.0 Hz, 1H), 7.19 (d,
J = 8.8 Hz, 2H), 6.98 (d, J = 9.2 Hz, 2H), 6.95 (d, J = 8.8 Hz, 2H), 3.85 (s, 3H), 3.84
(s, 3H), 2.30 (s, 3H); 13C NMR (100 MHz, CDCl3): d 163.29, 159.16, 146.37,
140.45, 137.04, 133.45, 132.44, 130.67, 129.98 (2Â), 129.84 (2Â), 128.90,
124.69, 114.48 (2Â), 113.75 (2Â), 55.62, 55.30, 20.66. Single-crystal X-ray
diagram: crystal of 3j was grown by slow diffusion of EtOAc into a solution of
3j in CH2Cl2 to yield colorless prisms. The compound crystallizes in the triclinic
crystal system, space group P-1
,
a = 8.2608(9) Å, b = 10.2952(12) Å,
c = 11.2990(13) Å, V = 900.77(18) Å3, Z = 2, dcalcd = 1.358 g/cm3, F(000) = 388,
2h range 1.90–26.39°, R indices (all data) R1 = 0.0650, wR2 = 0.1735. For 3l:
Yield = 76% (271 mg); mp = 133–135 °C (recrystallized from hexanes and
EtOAc); HRMS (ESI, M++1) calcd for C20H18FO3S 357.0961, found 357.0968; 1
H
NMR (400 MHz, CDCl3): d 7.92 (d, J = 8.8 Hz, 2H), 7.80 (d, J = 2.0 Hz, 1H), 7.72
(dd, J = 2.0, 8.0 Hz, 1H), 7.29 (d, J = 8.0 Hz, 1H), 7.24–7.19 (m, 2H), 7.14–7.09
(m, 2H), 6.99 (d, J = 8.8 Hz, 2H), 3.85 (s, 3H), 2.28 (s, 3H); 13C NMR (100 MHz,
CDCl3): d 162.35 (d, J = 245.6 Hz), 163.37, 145.61, 141.09, 137.05, 136.07,
133.28, 130.62, 130.43 (d, J = 7.6 Hz, 2Â), 129.89 (2Â), 128.94, 124.76, 115.35
(d, J = 21.2 Hz, 2Â), 114.52 (2Â), 55.63, 20.53. Single-crystal X-ray diagram:
crystal of 3l was grown by slow diffusion of EtOAc into a solution of 3l in
CH2Cl2 to yield colorless prisms. The compound crystallizes in the triclinic
crystal system, space group P-1, a = 7.6155(3) Å, b = 10.3670(18) Å,
c = 11.226(2) Å, V = 835.7(3) Å3, Z = 2, dcalcd = 1.416 g/cm3, F(000) = 372, 2h
range 1.90–26.56°, R indices (all data) R1 = 0.0395, wR2 = 0.0838.
6. (a) Oae, S. In Organic Sulfur Chemistry; Negishi, E., Ed.; CRC Press: Boca Raton, FL,
1992. Chapter 4 and Chapter 6; (b) Ogura, K.; Takeda, M.; Xie, J. R.; Akazome,
M.; Matsumoto, S. Tetrahedron Lett. 1923, 2001, 42; (c) Lim, C. H.; Kim, S. H.;
Kim, K. H.; Kim, J. N. Tetrahedron Lett. 2013, 54, 2476; (d) Vincze, Z.; Nemes, P.
Tetrahedron 2013, 69, 6269; (e) Diallo, A.; Zhao, Y.-L.; Wang, H.; Li, S.-S.; Ren, C.-
Q.; Liu, Q. Org. Lett. 2012, 14, 5776.
7. (a) Graybill, B. M. J. Org. Chem. 1967, 32, 2931; (b) Ueda, M.; Uchiyama, K.;
Kano, T. Synthesis 1984, 323.
8. (a) Nara, S. J.; Harjani, J. R.; Salunkhe, M. M. J. Org. Chem. 2001, 66, 8616; (b)
Frost, C. G.; Hartley, J. P.; Whittle, A. J. Synlett 2001, 830; (c) Bandgar, B. P.;
Kasture, S. P. Synth. Commun. 2001, 31, 1065.
9. Narkevitch, V.; Schenk, K.; Vogel, P. Angew. Chem., Int. Ed. 2000, 39, 1806; (b)
Narkevitch, V.; Megevand, S.; Schenk, K.; Vogel, P. J. Org. Chem. 2001, 66, 5080;
(c) Bouchez, L.; Vogel, P. Synthesis 2002, 225; (d) Huang, X.-G.; Vogel, P.
Synthesis 2002, 232; (e) Narkevitch, V.; Vogel, P.; Schenk, K. Helv. Chim. Acta
2002, 85, 1674; (f) Bouchez, L. C.; Dubbaka, S. R.; Turks, M.; Vogel, P. J. Org.
Chem. 2004, 69, 6413; (g) Bouchez, L. C.; Turks, M.; Bubbaka, S. R.; Fonquerne,
F.; Craita, C.; Laclef; Vogel, S. P. Tetrahedron 2005, 61, 11473; (h) Bouchez, L. C.;
Craita, C.; Vogel, P. Org. Lett. 2005, 7, 897.
15. CCDC 965537 (2k), 936536 (3b), 947226 (3j), 948270 (3l) and 965538 (3w)
contain the supplementary crystallographic data for this paper. This data can
be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or
from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033;
e-mail: deposit@ccdc.cam.ac.uk).
16. (a) Padwa, A.; Kline, D. N.; Murphree, S. S.; Yeske, P. E. J. Org. Chem. 1992, 57,
298; (b) Padwa, A.; Kline, D. N.; Noman, B. H. Tetrahedron Lett. 1988, 29, 265; (c)
Padwa, A.; Yeske, P. E. J. Am. Chem. Soc. 1988, 110, 1617; (d) Padwa, A.;
Murphree, S. S.; Yeske, P. E. Tetrahedron Lett. 1990, 31, 2983.
10. (a) Baarschers, W. H. Can. J. Chem. 1976, 54, 3056; (b) Kar, A.; Sayyed, I. A.; Lo,
W. F.; Kaiser, H. M.; Beller, M.; Tse, M. K. Org. Lett. 2007, 9, 3405; (c) Zhu, W.;