C
B. R. Brutiu et al.
Cluster
Synlett
Supporting Information
(10) (a) Cogan, D. A.; Ellman, J. A. J. Am. Chem. Soc. 1999, 121, 268.
(b) Kochi, T.; Tang, T. P.; Ellman, J. A. J. Am. Chem. Soc. 2003, 125,
11276.
(11) Hamel, P.; Zajac, N.; Atkinson, J. G.; Girard, Y. J. Org. Chem. 1994,
59, 6372.
Supporting information for this article is available online at
S
u
p
p
orit
n
gInformati
o
n
S
u
p
p
orti
n
gInformati
o
n
(12) For representative examples of sulfoxide removal in total syn-
thesis using Raney-nickel, see: (a) Klein, L. L. J. Am. Chem. Soc.
1985, 107, 2573. (b) Ohshima, T.; Xu, Y.; Takita, R.; Shimizu, S.;
Zhong, D.; Shibasaki, M. J. Am. Chem. Soc. 2002, 124, 14546.
(c) Carreño, M. C.; Des Mazery, R.; Urbano, A.; Colobert, F.;
Solladié, G. Org. Lett. 2004, 6, 297.
(13) For representative examples of sulfoxide removal in total syn-
thesis using t-BuLi, see: (a) Mastranzo, V. M.; Yuste, F.; Ortiz, B.;
Sánchez-Obregón, R.; Toscano, R. A.; García Ruano, J. L. J. Org.
Chem. 2011, 76, 5036. (b) Takiguchi, H.; Ohmori, K.; Suzuki, K.
Chem. Lett. 2011, 40, 1069. (c) Vakiti, J. R.; Ghosh, S. Tetrahedron
Lett. 2014, 55, 6438.
(14) Pons, A.; Michalland, J.; Zawodny, W.; Chen, Y.; Tona, V.;
Maulide, N. Angew. Chem. Int. Ed. 2019, 58, 17303.
(15) (a) Singh, P. K.; Field, L.; Sweetman, B. J. J. Org. Chem. 1988, 53,
2608. (b) Schöberl, A.; Gräfje, H. Justus Liebigs Ann. Chem. 1958,
617, 71.
References and Notes
(1) (a) Jia, T.; Wang, M.; Liao, J. Top. Curr. Chem. 2019, 377, 1.
(b) Trost, B.; Rao, M. Angew. Chem. Int. Ed. 2015, 54, 5026.
(c) Sipos, G.; Drinkel, E. E.; Dorta, R. Chem. Soc. Rev. 2015, 44,
3834. (d) Otocka, S.; Kwiatkowska, M.; Madalińska, L.;
Kiełbasiński, P. Chem. Rev. 2017, 117, 4147.
(2) (a) Frey, J.; Jerhaoui, S.; Choppin, S.; Wencel-Delord, J.; Colobert,
F. ACS Catal. 2018, 8, 2805. (b) Aitken, H. R. M.; Furkert, D. P.;
Hubert, J. G.; Wood, J. M.; Brimble, M. A. Org. Biomol. Chem.
2013, 11, 5147. (c) Motohashi, S.; Nagase, K.; Nakakita, T.;
Matsuo, T.; Yoshida, Y.; Kawakubo, T.; Miura, M.; Toriyama, M.;
Barybin, M. V. J. Org. Chem. 2011, 76, 3922.
(3) (a) Tang, K.-X.; Wang, C.-M.; Gao, T.-H.; Chen, L.; Fan, L.; Sun, L.-
P. Adv. Synth. Catal. 2019, 361, 26. (b) Pulis, A. P.; Procter, D. J.
Angew. Chem. Int. Ed. 2016, 55, 9842.
(4) (a) Kaiser, D.; Klose, I.; Oost, R.; Neuhaus, J.; Maulide, N. Chem.
Rev. 2019, 119, 8701. (b) Yanagi, T.; Nogi, K.; Yorimitsu, H. Tetra-
hedron Lett. 2018, 59, 2951.
(5) Maryasin, B.; Kaldre, D.; Galaverna, R.; Klose, I.; Ruider, S.;
Drescher, M.; Kählig, H.; González, L.; Eberlin, M.; Jurberg, I.;
Maulide, N. Chem. Sci. 2018, 9, 4124.
(6) Yanagi, T.; Nogi, K.; Yorimitsu, H. Chem. Eur. J. 2020, 26, 783.
(7) (a) Kaldre, D.; Maryasin, B.; Kaiser, D.; Gajsek, O.; Gonzalez, L.;
Maulide, N. Angew. Chem Int. Ed. 2017, 56, 2212. (b) Kaldre, D.;
Klose, I.; Maulide, N. Science 2018, 361, 664.
(16) Protodesulfination; General Procedure
To a solution of the sulfoxide (0.2 mmol, 1.0 equiv) and 1-octan-
ethiol (0.8 mmol, 4.0 equiv) in CH2Cl2 (0.2 M) in a vial, trifluoro-
methanesulfonic acid (0.1 mmol, 0.5 equiv) was added and the
mixture was stirred for 12 h at 23 °C. The reaction was
quenched by the addition of solid NaHCO3, stirred at 23 °C for
10 min, filtered and extracted with CH2Cl2. The resulting
organic phase was dried over MgSO4 and concentrated under
reduced pressure to give a crude product that was purified by
column chromatography (heptane/ethyl acetate).
(8) Otsuka, S.; Nogi, K.; Yorimitsu, H. Top. Curr. Chem. 2018, 376, 13.
(9) (a) Lindner, O.; Rodefeld, L. In Ullmann’s Encyclopedia of Indus-
trial Chemistry; Wiley-VCH: Weinheim, 2010, 269.
(b) Grundmann, C. In Houben-Weyl Methods of Organic Chemis-
try, 4th ed., Vol. 5/2b; Blome, H.; Clar, E.; Fiege, H.; Garratt, P. J.;
Grundmann, C.; Gundermann, K.-D.; Padeken, H.-G.; Pauson, P.
L.; Voelter, W.; Zander, M.; Zeller, K.-P., Ed.; Georg Thieme
Verlag: Stuttgart, 1981, 354. (c) For acid-promoted C–S bond
cleavage in sulfoximines, see: Wiezorek, S.; Lamers, P.; Bolm, C.
Chem. Soc. Rev. 2019, 48, 5408.
(17) 1,3,5-Trimethoxy-2-(methylsulfinyl)benzene (1b)
IR (neat): 2943, 1582, 1465, 1458, 1436, 1412, 1340, 1230,
1208, 1187, 1162, 1125, 1086, 1026 cm–1 1H NMR (600 MHz,
.
CDCl3): = 6.12 (s, 2 H), 3.88 (s, 6 H), 3.84 (s, 3 H), 3.04 (s, 3 H).
13C NMR (150 MHz, CDCl3): = 164.7, 161.3, 111.5, 91.3, 56.3,
55.7, 38.0. HRMS (ESI+): m/z [M + Na]+ calcd for C10H14O4SNa:
253.0505; found: 253.0512.
© 2020. Thieme. All rights reserved. Synlett 2020, 31, A–C