Synlett, Table of Contents Synlett 2023; 34(11): 1270-1274DOI: 10.1055/a-2012-0097 letter NIS-Mediated Oxidation of Hydrazones: A Rapid Access to Fused Lactones and Tosylhydrazides Ahmad Takallou a Natural and Medical Sciences Research Center, University of Nizwa, P.O. Box 33, Postal Code 616, Birkat Al Mauz, Nizwa, Sultanate of Oman , Sulaiman Al-Shidhani a Natural and Medical Sciences Research Center, University of Nizwa, P.O. Box 33, Postal Code 616, Birkat Al Mauz, Nizwa, Sultanate of Oman , Munir Al-Siyabi a Natural and Medical Sciences Research Center, University of Nizwa, P.O. Box 33, Postal Code 616, Birkat Al Mauz, Nizwa, Sultanate of Oman , Akbar Mobaraki b Department of Chemistry, Kharazmi University, South Mofatteh Ave., Tehran 15719-14911, Iran , Muhammad U. Anwar a Natural and Medical Sciences Research Center, University of Nizwa, P.O. Box 33, Postal Code 616, Birkat Al Mauz, Nizwa, Sultanate of Oman , Ahmed Al-Harrasi∗ a Natural and Medical Sciences Research Center, University of Nizwa, P.O. Box 33, Postal Code 616, Birkat Al Mauz, Nizwa, Sultanate of Oman › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract A tandem one-pot strategy for the synthesis of 4-iodo-3-aryl(alkyl)-1H-pyrano[4,3-b]quinolin-1-ones and (E)-3-(iodo(phenyl)methylene)isobenzofuran-1-(3H)-ones from 2-alkynylhydrazones has been developed through oxidation and regioselective 6-endo- and 5-exo-iodocyclization pathways by using NIS as an iodinating reagent. This approach tolerates a variety of in situ generated alkynyl-containing tosylhydrazones and affords the corresponding products in high yields. The protocol has also been applied for the synthesis of different derivatives in good to excellent yields. Key words Key wordstandem reactions - N-iodosuccinimide - lactones - tosylhydrazones - alkynes - oxidation Full Text References References and Notes 1a Zhu C, Wang R, Falck JR. Chem. Asian J. 2012; 7: 1502 1b Zhu D.-Y, Fang L, Han H, Wang Y, Xia J.-B. Org. Lett. 2017; 19: 4259 1c Zhang Z, Ju T, Ye J.-H, Yu D.-G. Synlett 2017; 28: 741 1d Singh J, Nickel GA, Cai Y, Jones DD, Nelson TJ, Small JE, Castle SL. Org. Lett. 2021; 23: 3970 1e Yu W, Zhang X, Liu C, Zhang Y, Gu X, Liao J, Zhang Z, Wei W, Li G, Liang T. J. Org. Chem. 2022; 87: 12424 1f Kantak AA, Potavathri S, Barham RA, Romano KM, DeBoef B. J. Am. Chem. Soc. 2011; 133: 19960 1g Kunchur HS, Balakrishna MS. Inorg. Chem. 2022; 61: 857 1h Devlin R, Jones DJ, McGlacken GP. Org. Lett. 2020; 22: 5223 1i Okuma K, Itoyama R, Sou A, Nagahoraa N, Shioj K. Chem. Commun. 2012; 48: 11145 1j Tang T.-M, Liu M, Wu H, Gou T, Hu X, Wang B.-Q, Hu P, Song F, Huang G. Org. Chem. Front. 2021; 8: 3867 2a Gore S, Baskaran S, König B. Org. Lett. 2012; 14: 4568 2b Dočekal V, Vopálenská A, Měrka P, Konečná K, Jand’ourek O, Pour M, Císařová I, Veselý J. J. Org. Chem. 2021; 86: 12623 2c Panther J, Müller TJ. J. Synthesis 2016; 48: 974 2d Park I.-K, Suh S.-E, Lim B.-Y, Cho C.-G. Org. Lett. 2009; 11: 5454 2e Dai X.-J, Li C.-J. J. Am. Chem. Soc. 2016; 138: 5344 2f Cranwell PB, Russell AT, Smith CD. Synlett 2016; 27: 131 2g Ojha DP, Prabhu KR. Org. Lett. 2015; 17: 18 3a Chen J.-R, Yu X.-Y, Xiao W.-J. Synthesis 2015; 47: 604 3b Galloway WR. J. D, Llobet AI, Spring DR. Nat. Commun. 2010; 1: 80 3c Schreiber SL. Nature 2009; 457: 153 3d Shi Z, Wang L, Yang Z, Jie L, Liu X, Cui X. J. Org. Chem. 2020; 85: 3029 3e Wu P, Zhang Y, Cheng Y. J. Org. Chem. 2022; 87: 2779 3f Qiu G, Wu J. Chem. Rec. 2016; 16: 19 3g Montgomery J. Angew. Chem. Int. Ed. 2004; 43: 3890 3h Enders DC, Grondal MR, Huttl M. Angew. Chem. Int. Ed. 2007; 46: 1570 3i Tietze LF, Dufert A, Lotz F, Solter L, Oum K, Lenzer T, Beck T, Herbst-Irmer R. J. Am. Chem. Soc. 2009; 131: 17879 4a Ding Q, Chen Z, Yu X, Peng Y, Wu J. Tetrahedron Lett. 2009; 50: 340 4b Yao H.-F, Wang D.-L, Li F.-H, Wu B, Cai Z.-J, Ji S.-J. Org. Biomol. Chem. 2020; 18: 7577 4c Jiang L, Yu X, Fang B, Wu J. Org. Biomol. Chem. 2012; 10: 8102 4d Li S, Luo Y, Wu J. Org. Lett. 2011; 13: 4312 4e Özer MS, Menges N, Keskin S, Şahin E, Balci M. Org. Lett. 2016; 18: 408 5 Chen Z, Ding Q, Yu X, Wu J. Adv. Synth. Catal. 2009; 351: 1692 6a Verma AK, Rustagi V, Aggarwal T, Singh AP. J. Org. Chem. 2010; 75: 7691 6b Takallou A, Al-Shidhani S, Anwar MU, Al-Harrasi A. Synthesis 2023; 55: 489 6c Reddy MB, Peri R, Bhagavathiachari M, Anandhan R. Org. Biomol. Chem. 2021; 19: 6792 6d Wang R.-X, Yuan S.-T, Liu J.-B, Wu J, Qiu G. Org. Biomol. Chem. 2018; 16: 4501 6e Verma AK, Aggarwal T, Rustagia V, Larock RC. Chem. Commun. 2010; 46: 4064 6f Zhu Y, Shen Z. Adv. Synth. Catal. 2017; 359: 3515 6g Biagetti M, Bellina F, Carpita A, Stabile P, Rossi R. Tetrahedron 2002; 58: 5023 6h Wang Y.-H, Liu J.-B, Ouyang B, Zhou H, Qiu G. Tetrahedron 2018; 74: 4429 7a Ye S, Wang H, Wu J. Eur. J. Org. Chem. 2010; 6436 7b Xiao Q, Ye S, Wu J. Org. Lett. 2012; 14: 3430 7c Nikbakht A, Balalaie S, Breit B. Org. Lett. 2019; 21: 7645 7d Ren H, Luo Y, Ye S, Wu J. Org. Lett. 2011; 13: 2552 7e Ye S, Gao K, Wu J. Adv. Synth. Catal. 2010; 352: 1746 7f Araujo DR, Goulart HA, Barcellos AM, Cargnelutti R, Lenardão EJ, Perin G. J. Org. Chem. 2020; 86: 1721 7g Han D, He Q, Fan R. Angew. Chem. Int. Ed. 2015; 54: 14013 7h He L, Nie H, Qiu G, Gao Y, Wu J. Org. Biomol. Chem. 2014; 12: 9045 8 4-Iodo-3-aryl(alkyl)-1H-pyrano[4,3-b]quinolin-1-ones: A mixture of 2-alkynylarylaldehydes (1.0 mmol, 1.0 equiv) and TsNHNH2 (1.0 mmol, 1.0 equiv) in DMF (2 mL) was stirred at 75 °C for 20 min. The mixture was then cooled to –5 °C in an ice/salt bath. Subsequently, NIS (2.2 mmol, 2.20 equiv) was added in portions over 5 min, and the mixture was slowly warmed to room temperature. The progress of reaction was monitored by TLC. After completion of the reaction, a solution of sodium thiosulfate was added to the reaction mixture to neutralize excess NIS. Then, H2O (5 mL) was added, the resulting mixture was extracted with ethyl acetate (3 × 5 mL), and the organic layer was washed with brine, dried over MgSO4 and concentrated in vacuo. This was followed by purification over silica gel, which provided the corresponding product. 4-Iodo-3-phenyl-1H-pyrano[4,3-b]quinolin-1-one (2a): Yellow oil; yield: 327 mg (82%). IR (KBr): 3150, 1711, 1526, 1118, 756 cm–1. 1H NMR (600 MHz, CDCl3): δ = 9.16 (s, 1 H), 8.32–8.30 (m, 1 H), 8.08–8.06 (m, 1 H), 7.97–7.90 (m, 4 H), 7.77–7.73 (m, 2 H), 7.70–7.68 (m, 1 H). 13C NMR (151 MHz, CDCl3): δ = 161.3, 156.0, 151.7, 150.1, 140.9, 133.8, 130.5, 129.7, 129.1, 128.1, 127.6, 125.2, 125.1, 114.2, 82.8. HRMS (ESI): m/z calcd for C18H10INO2 [M + H]+: 399.9834; found: 399.9831. Supplementary Material Supplementary Material Supporting Information CIF File
