Synlett 2018; 29(06): 830-834
DOI: 10.1055/s-0036-1589160
letter
© Georg Thieme Verlag Stuttgart · New York

Direct Iodosulfonylation of Alkylynones with Sulfonylhydrazides and Iodine Pentoxide Leading to Multisubstituted α,β-Enones

Huanhuan Cui
a   Institute of Medicine and Material Applied Technologies, Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong, P. R. of China   Email: huawangqfnu@126.com
,
Chenglong He
a   Institute of Medicine and Material Applied Technologies, Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong, P. R. of China   Email: huawangqfnu@126.com
,
Daoshan Yang
a   Institute of Medicine and Material Applied Technologies, Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong, P. R. of China   Email: huawangqfnu@126.com
,
Huilan Yue
b   Key Laboratory of Tibetan Medicine Research, Northwest Institute of Plateau Biology, Chinese Academy of Sciences, Qinghai 810008, P. R. of China   Email: weiweiqfnu@163.com
,
Wei Wei*
a   Institute of Medicine and Material Applied Technologies, Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong, P. R. of China   Email: huawangqfnu@126.com
b   Key Laboratory of Tibetan Medicine Research, Northwest Institute of Plateau Biology, Chinese Academy of Sciences, Qinghai 810008, P. R. of China   Email: weiweiqfnu@163.com
,
Hua Wang*
a   Institute of Medicine and Material Applied Technologies, Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong, P. R. of China   Email: huawangqfnu@126.com
› Author Affiliations

This work was supported by the National Natural Science Foundation of China (No. 21302109, 21302110, 21375075, and 21675099), the Natural Science Foundation of Shandong Province (ZR2015JL004 and ZR2016JL012), and the Open Projects Program of the Key Laboratory of Tibetan Medicine Research, Chinese Academy of Sciences, National Training Programs of Innovation and Entrepreneurship for Undergraduates (201610446026).
Further Information

Publication History

Received: 17 October 2017

Accepted after revision: 06 December 2017

Publication Date:
19 January 2018 (online)


§ These authors contributed equally to this work

Abstract

A facile and efficient method has been developed for the construction of multisubstituted α,β-enones through the direct selective iodosulfonylation of alkylynones with sulfonylhydrazides and iodine pentoxide. The present methodology offers a simple and attractive approach to various multisubstituted α,β-enones in moderate to good yields with excellent stereo- and regioselectivities under the metal- and peroxide-free conditions.

Supporting Information

 
  • References and Notes

    • 1a Oppolzer W. In Comprehensive Organic Synthesis . vol. 5. Trost BM. Fleming I. Pergamon; Oxford: 1991: 315
    • 1b Sundararajan G. Prabagaran N. Org. Lett. 2001; 3: 389
    • 1c Li G. Gao J. Wei H.-X. Enright M. Org. Lett. 2000; 2: 617
    • 3a Nielsen AT. Houlihan WJ. InOrganic Reactions . vol. 16. John Wiley & Sons; New York: 1968: 1-438
    • 3b Stork G. Kraus GA. Garcia GA. J. Org. Chem. 1974; 39: 3459
    • 3c Kourouli T. Kefalas P. Ragoussis N. Ragoussis V. J. Org. Chem. 2002; 67: 4615
    • 4a Bartoli G. Bellucci MC. Petrini M. Marcantoni E. Sambri L. Torregiani E. Org. Lett. 2000; 2: 1791
    • 4b Cadierno V. Crochet P. Garcia-Garrido SE. Gimeno J. Dalton Trans. 2010; 4015; and references cited therein
    • 5a Wadsworth WS. In Organic Reactions . vol. 25. John Wiley & Sons; New York: 1977: 73-250
    • 5b Boutagy J. Thomas R. Chem. Rev. 1974; 74: 87
    • 5c Maryanoff BE. Reitz AB. Chem. Rev. 1989; 89: 863
    • 6a Huber T. Kaiser D. Rickmeier J. Magauer T. J. Org. Chem. 2015; 80: 2281
    • 6b Ciesielski J. Canterbury DP. Frontier AJ. Org. Lett. 2001; 3: 823
    • 6c Bertozzi F. Gustafsson M. Olsson R. Org. Lett. 2002; 4: 4333
    • 6d Yang S.-M. Kuo G.-H. Gaul MD. Murray WV. J. Org. Chem. 2016; 81: 3464

      For selected examples, see:
    • 7a Simpkins NS. Sulfones in Organic Synthesis . Pergamon Press; Oxford: 1993
    • 7b Wolf WM. J. Mol. Struct. 1999; 474: 113
    • 7c Petrov KG. Zhang Y. Carter M. Cockerill GS. Dickerson S. Gauthier CA. Guo Y. Mook RA. Rusnak DW. Walker AL. Wood ER. Lackey KE. Bioorg. Med. Chem. Lett. 2006; 16: 4686
    • 7d Noshi MN. El-Awa A. Torres E. Fuchs PL. J. Am. Chem. Soc. 2007; 129: 11242
    • 7e Desrosiers JN. Charette AB. Angew. Chem. Int. Ed. 2007; 46: 5955
    • 7f Ettari R. Nizi E. Di Francesco ME. Dude M.-A. Pradel G. Vicik R. Schirmeister T. Micale N. Grasso S. Zappala M. J. Med. Chem. 2008; 51: 988
    • 7g Kotha S. Chavan AS. J. Org. Chem. 2010; 75: 4319
    • 8a Kirihara M. Yamamoto J. Noguchi T. Hirai Y. Tetra­hedron Lett. 2009; 50: 1180
    • 8b Huang X. Duan DH. Zheng WX. J. Org. Chem. 2003; 68: 1958
    • 8c Lu Q. Zhang J. Wei F. Qi Y. Wang H. Liu Z. Lei AW. Angew. Chem. Int. Ed. 2013; 52: 7156
    • 8d Lu Q. Zhang J. Zhao G. Qi Y. Wang H. Lei AW. J. Am. Chem. Soc. 2013; 135: 11481
    • 8e Wei W. Li J. Yang D. Wen J. Jiao Y. You J. Wang H. Org. Biomol. Chem. 2014; 12: 1861
    • 8f Li X. Xu X. Hu P. Xiao X. Zhou C. J. Org. Chem. 2013; 78: 7343
    • 8g Shen T. Yuan Y. Song S. Jiao N. Chem. Commun. 2014; 4115
    • 9a Taniguchi N. Synlett 2011; 1308
    • 9b Nair V. Augustine A. Suja TD. Synthesis 2002; 2259
    • 9c Nair V. Augustine A. George TG. Nair LG. Tetrahedron Lett. 2001; 42: 6763
    • 9d Gao Y. Wu W. Huang Y. Huang K. Jiang H. Org. Chem. Front. 2014; 1: 361
    • 9e Li X. Shi X. Fang M. Xu X. J. Org. Chem. 2013; 78: 9499
    • 9f Li X. Xu S. Shi X. Tetrahedron Lett. 2013; 54: 3071
    • 9g Zeng X. Ilies L. Nakamura E. Org. Lett. 2012; 14: 954
    • 10a Katrum P. Chiamapanichayakul S. Korworapan K. Pohmakotr M. Reutrkul V. Jaipetch T. Kuhakarn C. Eur. J. Org. Chem. 2010; 5633
    • 10b Wei W. Wen J. Yang D. Jing H. You J. Wang H. RSC Adv. 2015; 5: 4416
    • 10c Liu X. Duan X. Pan Z. Han Y. Liang Y. Synlett 2005; 1752
    • 10d Fang Y. Luo Z. Xu X. RSC Adv. 2016; 6: 59661
    • 10e Wan J.-P. Hu D. Bai F. Wei L. Liu Y. RSC Adv. 2016; 6: 73132
  • 11 Taniguchi N. Tetrahedron 2014; 70: 1984
  • 12 After performing the experiments and while preparing this manuscript, Reddy and co-workers reported iodosulfonylation of internal alkynes to synthesize highly substituted multifunctional olefins by using TBHP (3 equiv) as the oxidant, see: Kumar R. Dwivedi V. Reddy MS. Adv. Synth. Catal. 2017; 359: 2847
    • 13a Wei W. Liu C. Yang D. Wen J. You J. Suo Y. Wang H. Chem. Commun. 2013; 10239
    • 13b Wei W. Wen J. Yang D. Du J. You J. Wang H. Green Chem. 2014; 16: 2988
    • 13c Wei W. Wen J. Yang D. Wu M. You J. Wang H. Org. Biomol. Chem. 2014; 12: 7678
    • 13d Wei W. Wen J. Yang D. Guo M. Wang Y. You J. Wang H. Chem. Commun. 2015; 768
    • 13e Wei W. Cui H. Yang D. Liu X. He C. Dai S. Wang H. Org. Chem. Front. 2017; 4: 26
    • 13f Wang L. Yue H. Yang D. Cui H. Zhu M. Wang J. Wei W. Wang H. J. Org. Chem. 2017; 82: 6857
    • 14a Hang Z. Li Z. Liu Z.-Q. Org. Lett. 2014; 16: 3648
    • 14b Zhang L. Li Z. Liu Z.-Q. Org. Lett. 2014; 16: 3688
    • 14c Wen J. Wei W. Xue S. Yang D. Lou Y. Gao C. Wang H. J. Org. Chem. 2015; 80: 4966
  • 15 Preparation of (E)-3-iodo-1,3-diphenyl-2-(phenylsulfonyl)prop-2-en-1-one (4aa): In a 25 mL round-bottomed flack, alkylynone 1a (0.125 mmol), sulfonylhydrazide 2a (0.375 mmol), I2O5 (3; 0.125 mmol), and DME (2 mL) were added. The reaction mixture was stirred at 80 °C for 12 h. After completion the reaction, the solvent was then removed under vacuum. The residue was purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give the desired product 4aa. Yield: 49 mg (83%). 1H NMR (CDCl3, 400 MHz): δ = 8.28 (d, J = 7.2 Hz, 2 H), 7.72 (t, J = 7.3 Hz, 1 H), 7.62 (t, J = 7.8 Hz, 2 H), 7.54 (t, J = 7.4 Hz, 1 H), 7.49 (d, J = 7.3 Hz, 2 H), 7.36–7.26 (m, 5 H), 7.17 (d, J = 6.6 Hz, 2 H); 13C NMR (CDCl3, 100 MHz): δ = 190.6, 149.3, 140.4, 140.0, 134.7, 133.8, 133.7, 130.3, 129.6, 129.3, 129.0, 128.8, 128.3, 128.0, 127.5; HRMS: m/z [M + Na]+ calcd. for C21H15IO3SNa: 496.9684; found: 496.9689.