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HS facilitates the nucleophilic substitution of 4a with NH3. On
the basis of the infrared (IR) spectroscopy for β-MnO2-HS with
adsorbed pyridine (Figs. S3 and S4, ESI†), β-MnO2-HS showed
bands around 1445 cm–1, which were assignable to the
adsorption of pyridine on Lewis acid sites,16 and the amount of
Lewis acid sites was 163 μmol g−1.§ In addition, the red-shift of
the original SO2 antisymmetric stretching mode of 4a (from
1149 cm–1 to 1127 cm–1)17 most likely indicates the interaction
of 4a with Lewis acid sites on the β-MnO2-HS surface, which
would facilitate the nucleophilic attack of NH3 on 4a. Therefore,
the strong oxidizing ability and Lewis acidity of β-MnO2-HS is
essential to the aerobic oxidation of 1a to 4a and the
nucleophilic substitution of 4a with NH3, respectively, and such
dual-functionality of β-MnO2-HS results in highly efficient one-
pot aerobic sulfonamidation from thiols, O2, and NH3.
the formation of S–N bond by the reactions of 5a with NH3 was
DOI: 10.1039/C9CC09411C
25 kJ mol–1 and lower than that (49 kJ mol–1) of 3a, and (iii) the
S–S bond distance of 5a (2.23 Å) was longer than that (2.08 Å) of
3a.
§ In this case, no band due to pyridinium ions bonded to the
Brønsted acid sites was observed around 1540 cm–1.
¶ The formation of 4a was hardly observed for the oxidation of 3a
without NH3 under the conditions of entry 9 in Table 1, which
indicates that the presence of NH3 likely plays an important role
in the oxidation of 3a into 4a.15
1
2
(a) M. Mariusz, K. Zbigniew, W. Waldemar, C. Mariangela, T.
S. Claudiu, K. Vladimir, U.-L. Zofia and K. Przemyslaw, Bioorg.
Med. Chem., 2015, 23, 1421–1429; (b) H. Diem, G. Matthias
and R. A. Wagner, Ullmann’s Encyclopedia of Industrial
Chemistry, Amino Resins, Wiley‐VCH, Weinheim, 2012, 3,
79–106; (c) D. F. Cadogan and C. J. Howick, Ullmann’s
Encyclopedia of Industrial Chemistry, Plasticizers, Wiley ‐
VCH, Weinheim, 2012, 27, 599–618.
(a) M. Harmata, P. Zheng, C. Huang, M. G. Gomes, W. Jing, K.
Ranyanil, G. Balan and N. L. Calkins, J. Org. Chem., 2007, 72,
683–685; (b) F. Tamaddon, M. R. Sabeti, A. A. Jafari, F. Tirgir
and E. Kes M. Nasrollahzadeh, A. Ehsani and A. Rostami-
Vartouni, Appl. Organomet. Chem., 2016, 30, 125–131.
(a) S. Yea and J. Wu, Chem. Commun., 2012, 48, 7753–7755;
(b) Y. Chen, P. R. D. Murray, A. T. Davies and M. C. Willis, J.
Am. Chem. Soc., 2018, 140, 8781−8787; (c) D. Zheng, Y. An, Z.
Li and J. Wu, Angew. Chem. Int. Ed., 2014, 53, 2451–2454.
(a) X. Tang, L. Huang, C. Qi, X. Wu, W. Wu and H. Jiang, Chem.
Commun., 2013, 49, 6102–6104; (b) K. Yang, M. Ke, Y. Lin, Q.
Song, Green Chem., 2015, 17, 1395–1399; (c) J. Zhao, J. Xu, J.
Chen, X. Wang and M. He, RSC Adv., 2014, 4, 64698–64701.
(a) S. Gajare, M. Jagadale, A. Naikwade and P. Bansode, Appl.
Organomet. Chem., 2019, 33, e4915; (b) C. You, F. Yao, T. Yana
and M. Cai, RSC Adv., 2016, 6, 43605–43612.
1/2O2
H2O
-MnO2
SH
S
S
2
3a
1a
O2
-MnO2
O
O
Mn
-MnO2
S
3
4
O
S
O
NH2
S
2a
+
4a
Ph
S
Ph
1a
S
O
O
NH3
Mn
-MnO2
5
6
Scheme 2 Proposed reaction mechanism for the one-pot
aerobic sulfonamidation of 1a to 2a with β-MnO2-HS.
(a) K. Bahrami, M. M. Khodaei and M. Soheilizad, Tetrahedron,
2012, 68, 5095–5101; (b) H. Veisi, Bull. Korean Chem. Soc.,
2012, 333–386; (c) M. Jereb and L. Hribernik, Green Chem.,
2017, 19, 2286–2295.
Conclusions
7
8
9
(a) J. T. Grant, J. M. Venegas, W. P. McDermott and I.
Hermans, Chem. Rev., 2018, 118, 2769−2815; (b) P. Hu, M.
Tan, L. Cheng, H. Zhao, R. Feng, W.-J. Gu and W. Han, Nat.
Commun., 2019, 10, 2425.
(a) B. Dutta, S. Biswas, V. Sharma, N. O. Savage, S. P. Alpay and
S. L. Suib, Angew. Chem. Int. Ed., 2016, 55, 2171–2175; (b) K.
Yamaguchi, Y. Wang, T. Oishi, Y. Kuroda and N. Mizuno,
Angew. Chem. Int. Ed., 2013, 52, 5627–5630.
In conclusion, β-MnO2-HS could heterogeneously catalyze the
aerobic oxidative sulfonamidation of various aromatic and
heteroaromatic thiols without the need for any additives. The
present system was reusable and could be applied to the large-
scale sulfonamidation of p-toluenethiol to give the industrially
important sulfonamide.
This work was supported in part by Grants-in-Aid
(18H01786) for JSPS Fellows and for Scientific Research from
MEXT of Japan, JACI The 7th Research Award for New Chemistry
and Technology 2018, and the “Creation of Life Innovative
Materials for Interdisciplinary and International Researcher
Development” programs of MEXT.
(a) A. Corma and H. García, Chem. Rev., 2002, 102, 3837–
3892; (b) X. Ren, Z. Zhang, Y. Wang, J. Lu, J. An, J. Zhang, M.
Wang, X. Wang and Y. Luo, RSC Adv., 2019, 9, 15229–15237.
10 S. Kawsaki, K. Kamata and M. Hara, ChemCatChem, 2016, 8,
3247–3253.
11 (a) S. Shibata, K. Sugahara, K. Kamata and M. Hara, Chem.
Comm., 2018, 54, 6772–6775; (b) K. Sugahara, K. Kamata, S.
Muratsugu and M. Hara, ACS Omega, 2017, 2, 1608–1616.
12 K. Kamata, K. Sugahara, Y. Kato, S. Muratsugu, Y. Kumagai, F.
Oba and M. Hara ACS Appl. Mater. Interfaces, 2018, 10,
23792–23801.
13 E. Hayashi, Y. Yamaguchi, K. Kamata, N. Tsunoda, Y. Kumagai,
F. Oba and M. Hara, J. Am. Chem. Soc., 2019, 141, 890–900.
14 E. Hayashi, T. Komanoya, K. Kamata and M. Hara,
ChemSusChem, 2017, 10, 654–658.
Conflicts of interest
There are no conflicts to declare.
15 Y. Wang, H. Kobayashi, K. Yamaguchi and N. Mizuno, Chem.
Commun., 2012, 48, 2642–2644
16 T. Komanoya, K. Nakajima, M. Kitano and M. Hara, J. Phys.
Chem. C, 2015, 119, 26540–26546.
Notes and references
‡ While S-phenyl benzenethiosulfinate (5a) formed by the
monooxygenation of 3a was not directly observed, 5a can be also
a possible intermediate in the same way as 4a because of the
following calculation results: (i) The oxidation of 3a to 4a was
4 | J. Name., 2012, 00, 1-3
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