NIS-Mediated Oxidation of Hydrazones: A Rapid Access to Fused Lactones and Tosylhydrazides

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

tandem reactions - N-iodosuccinimide - lactones - tosylhydrazones - alkynes - oxidation

Publication History

Received: 09 November 2022

Accepted after revision: 12 January 2023

Accepted Manuscript online:
12 January 2023

Article published online:
20 February 2023

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• 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.