Organic Letters
Letter
F.; Hernandez Linares, A.; Mastranzo, V. M.; Ortiz, B.; Sanchez-
Obregon, R.; Fraile, A.; Garcia Ruano, J. L. J. Org. Chem. 2011, 76,
4635. (c) Aziz, J.; Messaoudi, S.; Alami, M.; Hamze, A. Org. Biomol.
Chem. 2014, 12, 9743. (d) Lujan-Montelongo, J. A.; Estevez, A. O.;
Fleming, F. F. Eur. J. Org. Chem. 2015, 2015, 1602.
(3) Li, H. J.; Wang, R.; Gao, J.; Wang, Y. Y.; Luo, D. H.; Wu, Y. C.
Adv. Synth. Catal. 2015, 357, 1393.
(4) For leading references, see (a) Zhang, Y.; Chitale, S.; Goyal, N.;
Li, G.; Han, Z. S.; Shen, S.; Ma, S.; Grinberg, N.; Lee, H.; Lu, B. Z.;
nucleophilic displacement by the sulfonyl group 12 generates
sulfinate 13. In DMPU, which is known to stabilize ion-pairs
and increase the nucleophilicity of anions, the decomposition of
1s leads to sulfinate 3s exclusively whereas in toluene the
decomposition yields 12% of pyrazole 15 generated via
intramolecular [3 + 2]-cycloaddition17 reaction along with the
sulfinate 3s. This suggests that the sulfinate formation occurs
via rapid protonation of intermediate 9. In the cross over
experiment between N-sulfonylhydrazones 1f and 4f, cross over
products were observed suggesting that the reaction is likely
intermolecular in nature. Although ylide 2b could be recovered
partly after the reaction, the catalytic amount of the ylide is not
sufficient for effective transformation under the present reaction
conditions. Reaction of the N-sulfonylhydrazone 1a in the
presence of a phosphazene base, tert-butylimino-tri-
(pyrrolidino)phosphorane and sulfur ylide, methyl 2-(diphen-
yl-λ4-sulfanylidene)acetate did not yield sulfinate. Transition of
the phosphorus ylide 2b to its salt and vice versa is believed to
be responsible for the effective conversion of N-sulfonylhy-
drazones to sulfinates.
In summary, a convenient method for the decomposition of
N-sulfonylhydrazones to the corresponding sulfinates is
developed under neutral reaction conditions. The transition
metal and base free decomposition method is compatible with
other functional groups and generates sulfinates in good yields.
The O-allyl and O-propargyl salicylaldehyde derived N-
tosylhydrazones selectively generated the sulfinates and did
not produce [3 + 2]-cycloadducts, which are obtained
exclusively in the presence of a base. A more detailed
investigation on this method is going on in our laboratory.
Senanayake, C. H. J. Org. Chem. 2012, 77, 690. (b) Fernan
́
dez, I.;
Khiar, N. Chem. Rev. 2003, 103, 3651.
(5) (a) Kadari, L.; Radha Krishna, P.; Prapurna, Y. L. Adv. Synth.
Catal. 2016, 358, 3863. (b) Huang, M.; Hu, L.; Shen, H.; Liu, Q.;
Hussain, M. I.; Pan, J.; Xiong, Y. Green Chem. 2016, 18, 1874. (c) Du,
B. N.; Li, Z.; Qian, P.; Han, J. L.; Pan, Y. Chem. - Asian J. 2016, 11,
478. (d) Shyam, P. K.; Kim, Y. K.; Lee, C.; Jang, H.-Y. Adv. Synth.
Catal. 2016, 358, 56.
́
(6) For recent reviews, see (a) Barluenga, J.; Valdes, C. Angew. Chem.,
Int. Ed. 2011, 50, 7486. (b) Shao, Z.; Zhang, H. Chem. Soc. Rev. 2012,
41, 560. (c) Xiao, Q.; Zhang, Y.; Wang, J. B. Acc. Chem. Res. 2013, 46,
236. (d) Jadhav, A. P.; Ray, D.; Rao, V. U. B.; Singh, R. P. Eur. J. Org.
Chem. 2016, 2016, 2369.
(7) Barluenga, J.; Tomas
Chem. 2009, 1, 494.
(8) For a selected example, see Barluenga, J.; Tomas
Aznar, F.; Valdes, C. Angew. Chem., Int. Ed. 2010, 49, 4993.
(9) (a) Hamze, A.; Treguier, B.; Brion, J.-D.; Alami, M. Org. Biomol.
́ ́
-Gamasa, M.; Aznar, F.; Valdes, C. Nat.
́
-Gamasa, M.;
́
́
Chem. 2011, 9, 6200. (b) Aziz, J.; Brion, J. D.; Hamze, A.; Alami, M.
Adv. Synth. Catal. 2013, 355, 2417. (c) Roche, M.; Frison, G.; Brion, J.
D.; Provot, O.; Hamze, A.; Alami, M. J. Org. Chem. 2013, 78, 8485.
(d) Roche, M.; Bignon, J.; Brion, J. D.; Hamze, A.; Alami, M. J. Org.
Chem. 2014, 79, 7583.
(10) For selected examples, see (a) Feng, X.-W.; Wang, J.; Zhang, J.;
Yang, J.; Wang, N.; Yu, X.-Q. Org. Lett. 2010, 12, 4408. (b) Ding, Q.;
Cao, B.; Yuan, J.; Liu, X.; Peng, Y. Org. Biomol. Chem. 2011, 9, 748.
(c) Lin, Y.; Luo, P.; Zheng, Q.; Liu, Y.; Sang, X.; Ding, Q. RSC Adv.
2014, 4, 16855. (d) Mao, S.; Gao, Y.-R.; Zhu, X. Q.; Guo, D.-D.;
Wang, Y.-Q. Org. Lett. 2015, 17, 1692. (e) Li, L.-L.; Gao, L.-X.; Han,
F.-S. RSC Adv. 2015, 5, 29996. (f) Tsai, A. S.; Curto, J. M.; Rocke, B.
N.; Dechert-Schmitt, A. M. R.; Ingle, G. K.; Mascitti, V. Org. Lett.
2016, 18, 508.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Typical experimental procedure, characterization data
and copies of 1H NMR and 13C NMR spectra for all new
(11) Sha, Q.; Wei, Y. Tetrahedron 2013, 69, 3829.
(12) (a) Zhao, J. L.; Guo, S.-H.; Qiu, J.; Gou, X.-F.; Hua, C.-W.;
Chen, B. Tetrahedron Lett. 2016, 57, 2375. (b) Barluenga, J.; Tomas
́
-
Gamasa, M.; Aznar, F.; Valdes, C. Eur. J. Org. Chem. 2011, 2011, 1520.
́
(c) Feng, X. W.; Wang, J.; Zhang, J.; Yang, J.; Wang, N.; Yu, X. Q. Org.
Lett. 2010, 12, 4408. (d) Zhang, J. L.; Chan, P. W. H.; Che, C. M.
Tetrahedron Lett. 2003, 44, 8733.
AUTHOR INFORMATION
■
Corresponding Author
ORCID
(13) Bertha, F.; Keg
G.; Simig, G.; Volk, B. J. Org. Chem. 2017, 82, 1895.
́ ́ ́ ́
l, T.; Fetter, J.; Molnar, B.; Dancso, A.; Nemeth,
(14) Choudhary, D.; Agrawal, C.; Khatri, V.; Thakuria, R.; Basak, A.
K. Tetrahedron Lett. 2017, 58, 1132.
(15) Allwood, D. M.; Blakemore, D. C.; Brown, A. D.; Ley, S. V. J.
Org. Chem. 2014, 79, 328.
Notes
The authors declare no competing financial interest.
(16) Kong, Y.; Zhang, W.; Tang, M.; Wang, H. Tetrahedron 2013, 69,
7487.
ACKNOWLEDGMENTS
■
(17) (a) Zheng, Y.; Zhang, X.; Yao, R.; Wen, Y. C.; Huang, J.; Xu, X.
J. Org. Chem. 2016, 81, 11072. (b) Divya, K. V. L.; Meena, A.; Suja, T.
D. Synthesis 2016, 48, 4207.
Research grants from SERB (Grant YSS/2014/000957) and
UGC (F.4-5/2006(BSR)), New Delhi, is gratefully acknowl-
edged. We thank MRC, MNIT Jaipur for recording the NMR
spectra. We also thank USIC, University of Rajasthan, Jaipur,
for the high-resolution mass spectrometry (HRMS) data.
REFERENCES
■
(1) For reviews on the synthesis and applications of sulfinates, see
(a) Fernandez, I.; Khiar, N. Chem. Rev. 2003, 103, 3651. (b) Robak, M.
T.; Herbage, M. A.; Ellman, J. A. Chem. Rev. 2010, 110, 3600.
(2) (a) Tapia-Pineda, A.; Perez-Arrieta, C.; Silva-Cuevas, C.; Paleo,
E.; Lujan-Montelongo, J. A. J. Chem. Educ. 2016, 93, 1470. (b) Yuste,
D
Org. Lett. XXXX, XXX, XXX−XXX