1,4,2-Dioxazol-5-ones as Isocyanate Equivalents: Chemoselective Non-Metal-Catalyzed Carboxamidation of Indoles

Anand Vala; Deepa Parmar; Rahul Rayani; Rakesh Kusurkar; Ramakrishna Guduru; Uttam Kaneriya; Uday Gondaliya; Nirali Parmar; Jigar Y. Soni

doi:10.1055/s-0041-1737338

Synlett, Table of Contents

Synlett 2022; 33(07): 689-693
DOI: 10.1055/s-0041-1737338

letter

1,4,2-Dioxazol-5-ones as Isocyanate Equivalents: Chemoselective Non-Metal-Catalyzed Carboxamidation of Indoles

Anand Vala

^aPiramal Discovery Solutions, Pharmaceutical Special Economic Zone, Sarkhej, Bavla Highway, Ahmedabad, Gujarat 38221, India

^bDepartment of Chemistry, Faculty of Science, The Madhav University, Pindwara (Sirohi)-307026, Rajasthan, India

,

Deepa Parmar

^aPiramal Discovery Solutions, Pharmaceutical Special Economic Zone, Sarkhej, Bavla Highway, Ahmedabad, Gujarat 38221, India

^bDepartment of Chemistry, Faculty of Science, The Madhav University, Pindwara (Sirohi)-307026, Rajasthan, India

,

Rahul Rayani

^aPiramal Discovery Solutions, Pharmaceutical Special Economic Zone, Sarkhej, Bavla Highway, Ahmedabad, Gujarat 38221, India

^bDepartment of Chemistry, Faculty of Science, The Madhav University, Pindwara (Sirohi)-307026, Rajasthan, India

,

Rakesh Kusurkar

^aPiramal Discovery Solutions, Pharmaceutical Special Economic Zone, Sarkhej, Bavla Highway, Ahmedabad, Gujarat 38221, India

^bDepartment of Chemistry, Faculty of Science, The Madhav University, Pindwara (Sirohi)-307026, Rajasthan, India

,

Ramakrishna Guduru

,

Uttam Kaneriya

^aPiramal Discovery Solutions, Pharmaceutical Special Economic Zone, Sarkhej, Bavla Highway, Ahmedabad, Gujarat 38221, India

,

Uday Gondaliya

^aPiramal Discovery Solutions, Pharmaceutical Special Economic Zone, Sarkhej, Bavla Highway, Ahmedabad, Gujarat 38221, India

,

Nirali Parmar

^aPiramal Discovery Solutions, Pharmaceutical Special Economic Zone, Sarkhej, Bavla Highway, Ahmedabad, Gujarat 38221, India

,

Jigar Y. Soni∗

^bDepartment of Chemistry, Faculty of Science, The Madhav University, Pindwara (Sirohi)-307026, Rajasthan, India

› Author Affiliations

Abstract

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Abstract

1,4,2-Dioxazol-5-ones are known to undergo decarboxylation under thermal conditions followed by Lossen’s rearrangement to give isocyanates. Described herein is the in situ trapping of the isocyanates by indoles to give indole-3-carboxamides in good to excellent yields.

Key words

dioxazolones - isocyanates - Lossen rearrangement - indolecarboxamides - metal-free reaction

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References

References and Notes

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18 N-Phenyl-1H-indole-3-carboxamide (3aa); Typical Procedure KO ^t Bu (20 mmol) was added in one portion to a stirred solution of 1H-indole (2a; 10 mmol) and 3-phenyl-1,4,2-dioxazol-5-one (1a; 12 mmol) in toluene (20 mL) at r.t., and the mixture was then stirred at 110 °C for 1–2 h until the reaction was complete (TLC). The mixture was cooled to r.t. and H₂O (20 mL) was then added. The resulting mixture was extracted with EtOAc (3 × 50 mL), and the extracts were dried (Na₂SO₄) and then concentrated under reduced pressure. The residue was purified by chromatography [silica gel, hexane–EtOAc (8:2)] to give a pale yellow solid; yield: 58 mg (57%); mp 172–174 °C. ¹H NMR (400 MHz, DMSO-d ₆): δ = 1.74 (br s, 1 H), 9.71 (br s, 1 H), 8.30 (d, J = 3.0 Hz, 1 H), 8.20 (d, J = 7.9 Hz, 1 H), 7.77 (d, J = 8.0 Hz, 2 H), 7.47 (d, J = 7.9 Hz, 1 H), 7.33 (t, J = 7.7 Hz, 2 H), 7.17 (m, 2 H), 7.04 (t, J = 7.4 Hz, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 163.73, 140.30, 136.69, 129.13, 128.99, 126.90, 123.05, 122.59, 121.56, 121.11, 120.20, 112.41, 110.97. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₅H₁₃N₂O: 237.1028; found: 237.1026.

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