K
C.-K. Chan et al.
Paper
Synthesis
and the solvent was concentrated. The residue was diluted with H2O
(10 mL) and the mixture was extracted with CH2Cl2 (3 × 20 mL). The
combined organic layers were washed with brine, dried, filtered and
evaporated under reduced pressure to afford the crude product. Puri-
fication on silica gel (hexanes/EtOAc, 8:1 to 4:1) afforded compound
13a.
Wang, J. Eur. J. Org. Chem. 2011, 30, 1015. (f) Doyle, M. P.; Duffy,
R.; Ratnikov, M.; Zhou, L. Chem. Rev. 2010, 110, 704. (g) Zhang,
Z.; Wang, J. Tetrahedron 2008, 64, 6577. (h) Maas, G. Chem. Soc.
Rev. 2004, 33, 183. (i) Ye, T.; McKervey, M. A. Chem. Rev. 1994,
94, 1091.
(2) Selected recent examples on the metal-mediated reactions of
diazo compounds follow. For CoIII, see: (a) Li, J.; Tang, M.; Zang,
L.; Zhang, X.; Zhang, Z.; Ackermann, L. Org. Lett. 2016, 18, 2742.
For PdII, see: (b) Belhomme, M.-C.; Wang, D.; Szabo, K. Org. Lett.
2016, 18, 2503. (c) Yuan, W.; Eriksson, L.; Szabo, K. Angew.
Chem. Int. Ed. 2016, 55, 8410. For IrIII, see: (d) Phatake, R. S.;
Patel, P.; Ramana, C. V. Org. Lett. 2016, 18, 292. For PdII/CrIII, see:
(e) Wang, P.-S.; Lin, H.-C.; Zhou, X.-L.; Gong, L.-Z. Org. Lett. 2014,
16, 3332. For FeI, see: (f) Ma, C.; Xing, D.; Zhai, C.; Che, J.; Liu, S.;
Wang, J.; Hu, W. Org. Lett. 2013, 15, 6140. For YIII, see:
(g) Gulevich, A. V.; Helan, V.; Wink, D. J.; Gevorgyan, V. Org. Lett.
2013, 15, 956. For CuII, see: (h) Luan, Y.; Schaus, S. E. Org. Lett.
2011, 13, 2510. (i) Kumar, R.; Verma, D.; Mobin, S. M.;
Namboothiri, I. N. N. Org. Lett. 2012, 14, 4070. (j) For a review,
see: Zhu, S.-F.; Zhou, Q.-L. Acc. Chem. Res. 2012, 45, 1365.
(3) For aziridination, see: (a) Lu, Z.; Zhang, Y.; Wulff, W. D. J. Am.
Chem. Soc. 2007, 129, 7185. (b) Zhang, Y.; Desai, A.; Lu, Z.; Hu,
G.; Ding, Z.; Wulff, W. D. Chem. Eur. J. 2008, 14, 3785. (c) Zhang,
Y.; Lu, Z.; Desai, A.; Wulff, W. D. Org. Lett. 2008, 10, 5429.
(4) For rearrangement, see: (a) Kirmse, W. Eur. J. Org. Chem. 2002,
21, 2193. (b) Candeias, N. R.; Afonso, C. A. M. Curr. Org. Chem.
2009, 13, 763.
(5) For cyclopropanation, see: (a) Doyle, M. P.; Protopopova, M. N.
Tetrahedron 1998, 54, 7919. (b) Lowenthal, R. E.; Masamune, S.
Tetrahedron Lett. 1991, 32, 7373. (c) Nishiyama, H.; Itoh, Y.;
Matsumoto, H.; Park, S. B.; Itoh, K. J. Am. Chem. Soc. 1994, 116,
2223. (d) Illa, O.; Rodriguez-García, C.; Acosta-Silva, C.; Favier, I.;
Picurelli, D.; Oliva, A.; Gomez, M.; Branchadell, V.; Ortuno, R. M.
Organometallics 2007, 26, 3306.
(6) For C–H bond insertion, see: (a) Chelucci, G.; Saba, A. Tetrahe-
dron Lett. 1995, 36, 4673. (b) Lombard, F. J.; Coster, M. J. Org.
Biomol. Chem. 2015, 13, 6419.
Yield: 7 mg (10%); colorless oil.
1H NMR (200 MHz, CDCl3): δ = 5.83 (s, 1 H), 2.65–2.59 (m, 4 H), 2.04–
1.99 (m, 2 H).
HRMS (ESI): m/z [M + 1]+ calcd for C6H8ClO2: 147.0213; found:
147.0218.
Toluene-4-thiosulfonic Acid S-p-Tolyl Ester (14)34
K2CO3 (207 mg, 1.5 mmol) was added to a solution of p-thiocresol
(100 mg, 0.8 mmol) in acetone (5 mL) at r.t. The reaction mixture was
stirred at r.t. for 10 min. Compound 7a (123 mg, 0.4 mmol) or 9a (140
mg, 0.4 mmol) in acetone (5 mL) was added to the reaction mixture at
r.t. The mixture was stirred at r.t. for 2 h. The residue was diluted with
H2O (10 mL) and the mixture was extracted with CH2Cl2 (3 × 20 mL).
The combined organic layers were washed with brine, dried, filtered
and evaporated under reduced pressure to afford the crude product.
Purification on silica gel (hexanes/EtOAc, 10:1 to 4:1) afforded 14.
Yield: from 7a: 17 mg (15%); from 9a: 14 mg (13%); colorless solid;
mp 77–79 °C (recrystallized from hexanes and EtOAc).
1H NMR (400 MHz, CDCl3): δ = 7.46 (d, J = 8.4 Hz, 2 H), 7.25–7.20 (m, 4
H), 7.14 (d, J = 8.4 Hz, 2 H), 2.42 (s, 3 H), 2.37 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 144.56, 142.01, 140.47, 136.46 (× 2),
130.16 (× 2), 129.34 (× 2), 127.57 (× 2), 124.58, 21.61, 21.44.
HRMS (ESI): m/z [M + 1]+ calcd for C14H15O2S2: 279.0514; found:
279.0521.
Single-crystal X-ray analysis: crystals of compound 14 were grown by
slow diffusion of EtOAc into a solution of compound 14 in CH2Cl2 to
yield colorless prisms. The compound crystallizes in the monoclinic
crystal system, space group P21/c, a = 13.121(2) Å, b = 6.4969(12) Å,
c = 15.180(3) Å, V = 1293.1(4) Å3, Z = 4, dcalcd = 1.430 mg/cm3, F(000) =
584, 2θ range 1.553~26.486o, R indices (all data), R1 = 0.0560, wR2 =
0.1027.
(7) For O–H bond insertion, see: (a) Aller, E.; Cox, G. G.; Miller, D. J.;
Moody, C. J. Tetrahedron Lett. 1994, 35, 5949. (b) Bernardim, B.;
Couch, E. D.; Hardman-Baldwin, A. M.; Burtoloso, A. C. B.;
Mattson, A. E. Synthesis 2016, 48, 677. (c) Miller, D. J.; Moody, C.
J. Tetrahedron 1995, 51, 10811. (d) Maier, T. C.; Fu, G. C. J. Am.
Chem. Soc. 2006, 128, 4594. (e) Zhu, S.-F.; Cai, Y.; Mao, H.-X.;
Xie, J.-H.; Zhou, Q.-L. Nat. Chem. 2010, 2, 546.
Acknowledgment
The authors would like to thank the Ministry of Science and Technol-
ogy of the Republic of China for financial support (MOST 105-2113-
M-037-001).
(8) For N–H bond insertion, see: (a) Davies, J. R.; Kane, P. D.;
Moody, C. J. Tetrahedron 2004, 60, 3967. (b) Lee, E. C.; Fu, G. C. J.
Am. Chem. Soc. 2007, 129, 12066. (c) Liu, B.; Zhu, S.-F.; Zhang,
W.; Chen, C.; Zhou, Q.-L. J. Am. Chem. Soc. 2007, 129, 5834.
(d) Xu, B.; Zhu, S.-F.; Xie, X.-L.; Shen, J.-J.; Zhou, Q.-L. Angew.
Chem. Int. Ed. 2011, 50, 11483. (e) Liu, B.; Zhu, S.-F.; Zhang, W.;
Chen, C.; Zhou, Q.-L. J. Am. Chem. Soc. 2007, 129, 5834.
(9) For S–H bond insertion, see: (a) Moyer, M. P.; Feldman, P. L.;
Rapoport, H. J. Org. Chem. 1985, 50, 5223. (b) Galardon, E.; Le
Maux, P.; Simonneaux, G. Tetrahedron 2000, 56, 615. (c) Xu, B.;
Zhu, S.-F.; Zhang, Z.-C.; Yu, Z.-X.; Ma, Y.; Zhou, Q.-L. Chem. Sci.
2014, 5, 1442.
Supporting Information
Supporting information for this article is available online at
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References
(10) For Bi(OTf)3, see: (a) Chang, M.-Y.; Cheng, Y.-C.; Lu, Y.-J. Org.
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(11) For In(OTf)3, see: Chang, M.-Y.; Lu, Y.-J.; Cheng, Y.-C. Tetrahedron
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(1) For reviews on the diazo compounds, see: (a) Candeias, N. R.;
Paterna, R.; Gois, P. M. P. Chem. Rev. 2016, 116, 2937. (b) Ford,
A.; Miel, H.; Ring, A.; Slattery, C. N.; Maguire, A. R.; McKervey, M.
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–L