8
M.A. Mehdid et al. / Tetrahedron xxx (2013) 1e8
(25 mg, 90%) as a pale yellow oil. Rf: 0.75 (CHCl3/AcOEt, 9:1). 1H
NMR (300 MHz, CDCl3):
¼4.33 (s, 2H, CH2), 7.25e7.48 (m, 7H, Ar),
7.54e7.60 (m, 1H, Ar), 7.96e7.99 (m, 2H, Ar). 13C NMR (75 MHz,
CDCl3):
133.4, 136.8, 137.5, 191.3. HRMS m/z calculated for C14H12OS
[MþH]þ: 229.0682; found: 229.0680.
(sept, 1H, J¼3.6 Hz), 127.3 (q, 2C, J¼3.2 Hz), 127.8, 128.8 (2C), 129.0
(2C), 132.4 (q, 2C, J¼34.2 Hz), 136.4, 138.4, 188.9. HRMS m/z calcu-
lated for C16H10OSF6 [MþI]ꢀ: 490.9407; found: 490.9411.
d
d
¼33.3, 127.3 (2C), 127.3, 128.6 (2C), 128.6 (2C), 129.0 (2C),
Acknowledgements
M.A.M. is grateful to BFA program (FrencheAlgerian exchange
program) for grant. J.N. would like to thank Cusanuswerk for
funding. V. Monnier and C. Chendo are thanked for HMRS
experiments.
5.4.1.4. S-Methyl
(3b1). A solution of thiazolium salt 1b1 (106 mg, 0.22 mmol) and
triethylamine (31 L, 0.22 mmol) in acetonitrile (5 mL) was stirred
3,5-bis(trifluoromethyl)benzenecarbothioate
m
at room temperature for 2 h. The solvent was evaporated in vacuo
and the crude product was purified by chromatography (CHCl3/
AcOEt, 9:1) to give 3b1 (30 mg, 83%) as a pale yellow oil. Rf: 0.76
Supplementary data
(CHCl3/AcOEt 9:1). 1H NMR (300 MHz, CDCl3):
d
¼2.56 (s, 3H, CH3),
X-ray data for 6a and 6d, 1H and 13C NMR spectra of the com-
pounds. HPLC on chiral support of 6e. 1H NMR of cross-coupling
experiments. Supplementary data associated with this article can
8.07 (s, 1H, Ar), 8.39 (s, 2H, Ar). 13C NMR (75 MHz, CDCl3):
d
¼12.0,
122.8 (q, 2C, J¼273.0 Hz), 126.3e126.5 (sept, 1H, J¼3.5 Hz), 127.2
(q, 2C, J¼3.2 Hz), 132.4 (q, 2C, J¼34.2 Hz), 138.6, 189.9. HMRS:
ionization of the sample under various conditions failed.
5.4.1.5. S-Ethyl
(3b2). A solution of thiazolium salt 1b2 (116 mg, 0.19 mmol) and
triethylamine (26 L, 0.19 mmol) in acetonitrile (5 mL) was stirred
at room temperature for 2 h. The solvent was evaporated in vacuo
and the crude product was purified by chromatography (CHCl3/
AcOEt, 9:1) to give 3b2 (52.5 mg, 93%) as a pale yellow oil. Rf: 0.8
3,5-bis(trifluoromethyl)benzenecarbothioate
References and notes
m
1. Roussel, C.; Andreoli, F.; Roman, M.; Hristova, M.; Vanthuyne, N. Molecules
2005, 10, 327e333.
2. Part I: Mehdid, M. A.; Djafri, A.; Roussel, C.; Andreoli, F. Molecules 2009, 14,
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4. (a) Bellec, N.; Lorcy, D.; Robert, A. Synthesis 1998, 1442e1446; (b) Vanthuyne, N.;
Andreoli, F.;Fernandez, S.; Roman, M.; Roussel, C. Lett. Org. Chem. 2005, 2, 433e443.
5. For instance, the enantiomers of 6a were baseline resolved (
89) on Chiralpak AD column using 70:30 hexane/2-PrOH mixture as eluent. The
barrier to rotation is fairly large (>140 kJ/mol in CHCl3 at 61 ꢁC.) Review on
atropisomerism in heterocyclic frameworks: Alkorta, I.; Elguero, J.; Roussel, C.;
Vanthuyne, N.; Piras, P. Adv. Heterocycl. Chem. 2012, 105, 1e188.
(CHCl3/AcOEt 9:1). 1H NMR (300 MHz, CDCl3):
d
¼1.39 (t, 3H,
J¼7.4 Hz, CH3), 3.16 (q, 2H, J¼7.4 Hz, CH2), 8.06 (s, 1H, Ar), 8.38 (s,
2H, Ar). 13C NMR (75 MHz, CDCl3):
d
¼14.5, 24.1, 122.8 (q, 2C,
a¼1.23 and Rs¼1.
J¼273 Hz), 126.2e126.4 (sept, 1H, J¼3.6 Hz), 127.2 (q, 2C, J¼3.2 Hz),
132.4 (q, 2C, J¼34.1 Hz), 138.8, 189.6. HRMS m/z calculated for
C
11H8OSF6 [MþAg]þ: 408.9246; found: 408.9247.
6. (a) Steele, R.; Monti, C.; Gennari, C.; Piarulli, U.; Andreoli, F.; Vanthuyne, N.;
Roussel, C. Tetrahedron: Asymmetry 2006, 17, 999e1006; (b) Roussel, C.; Roman,
M.; Andreoli, F.; Del Rio, A.; Faure, R.; Vanthuyne, N. Chirality 2006, 18,
762e771; (c) Roussel, C.; Kaid-Slimane, R.; Andreoli, F.; Renaudin, M.; Van-
thuyne, N. Chirality 2009, 21, 160e166.
5.4.1.6. rac-S-3,7-Dimethyloct-6-en-1-yl ethanethioate (3c).23
A
solution of thiazolium salt 1c (190 mg, 0.47 mmol) and triethylamine
(66 L, 0.47 mmol) in acetonitrile (5 mL) was stirred at room tem-
m
perature for 3 h. The solvent was evaporated in vacuo and the crude
product was purified by chromatography (CH2Cl2) to give 3c (64 mg,
64%) as a yellow oil. Rf: 0.76 (CH2Cl2). 1H NMR (400 MHz, CDCl3):
7. (a) Roussel, C.; Gallo, R.; Chanon, M.; Metzger, J. J. Chem. Soc., Perkin Trans. 2
(1972e1999) 1974, 1304e1306; (b) Datta, K. C.; Roussel, C.; Metzger, J. Bull. Soc.
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€
Sandstrom, J. J. Am. Chem. Soc. 1976, 98, 2847e2852; (d) Roussel, C.; Stein, J.-L.;
d
¼0.90 (d, 3H, J¼6.4 Hz, CH3), 1.11e1.21 (m, 1H, CH), 1.27e1.62 (m,
Beauvais, F. New J. Chem. 1990, 14, 169e173.
4H, 2CH2), 1.60 (s, 3H, CH3), 1.69 (s, 3H, CH3), 1.90e2.05 (m, 2H, CH2),
2.32 (s, 3H, COCH3), 2.83e2.98 (m, 2H, SCH2), 5.08 (tt, 1H, J¼1.2,
8. (a) Janssen, M. J. In The Chemistry of Carboxylic Acids and Esters; Patai, S., Ed.;
John Wiley and Sons: New York, NY, 1969; pp 705e764; (b) Cronyn, M. W.;
Chang, M. P.; Wall, R. A. J. Am. Chem. Soc. 1955, 77, 3031e3034.
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20b, pp 1597e1689.
10. Ralston, A. W.; Segebrecht, E. W.; Bauer, S. T. J. Org. Chem. 1939, 4, 502e505.
11. (a) Bandgar, B. P.; More, P. E.; Kamble, V. T.; Sawant, S. S. Aust. J. Chem. 2008, 61,
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1998, 877e878; (c) Silveira, C. C.; Braga, A. L.; Larghi, E. L. Organometallics 1999,
18, 5183e5186.
7.0 Hz, ]CH). 13C NMR (100 MHz, CDCl3):
d
¼17.6,19.1, 25.4, 25.7, 27.0,
30.6, 32.0, 36.5, 36.7, 124.6, 131.3, 196.0. HRMS m/z calculated for
C
12H22OS [MþH]þ: 215.1464; found: 215.1466.
5.4.1.7. S1,S5-Dimethyl pentanebis(thioate) (3e). A solution of
thiazolium salt 1e (117 mg, 0.21 mmol) and triethylamine (58 mL,
12. Qiu, R. H.; Xu, X. H.; Li, Y. H.; Shao, L. L.; Zhang, G. P.; An, D. L. Synth. Commun.
0.42 mmol) in acetonitrile (5 mL) was stirred at room temperature
for 2 h. The solvent was evaporated in vacuo and the crude product
was purified by chromatography (CHCl3) to give 3e (24 mg, 88%) as
2010, 40, 3309e3314.
13. (a) Takeda, K.; Tsuboyama, K.; Yamaguchi, K.; Ogura, H. J. Org. Chem. 1985, 50,
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an oil. Rf: 0.54 (CHCl3). 1H NMR (300 MHz, CDCl3)
d
¼2.03 (quint, 2H,
CH2), 2.30 (s, 6H, 2CH3), 2.62 (t, 4H, J¼7.3 Hz, 2CH2). 13C NMR
(75 MHz, CDCl3)
d
¼11.6 (2C), 21.3, 42.5 (2C), 198.9 (2C). HRMS m/z
calculated for C7H12O2S2 [MþNa]þ: 215.0171; found: 215.0171.
17. Kobayashi, Y.; Itabashi, K. Synthesis 1985, 671e672.
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necarbothioate (3b3) without isolation of the thiazolium salt 1b3. A
19. (a) Leclaire, J.; Vial, L.; Otto, S.; Sanders, J. K. M. Chem. Commun. 2005, 1959e1961;
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solution of amide 6b (80 mg, 0.17 mmol) and benzylbromide (20
0.17 mmol) in acetonitrile (5 mL) was refluxed for 24 h. After
cooling, triethylamine (24 L) was added and the solution stirred at
mL,
m
room temperature for 2 h. The solvent was evaporated in vacuo and
the crude product was purified by chromatography (CHCl3/AcOEt,
9:1) to give 3b3 (57 mg, 92%) as a pale yellow oil. Rf: 0.75 (CHCl3/
AcOEt, 9:1). 1H NMR (300 MHz, CDCl3):
d
¼4.39 (s, 2H, CH2),
7.28e7.40 (m, 5H, Ar), 8.06 (s, 1H, Ar), 8.39 (s, 2H, Ar). 13C NMR
(75 MHz, CDCl3):
¼33.9, 122.7 (q, 2C, J¼273.0 Hz), 126.5e126.6
d