An Efficient Direct Access to Carbamates from Alcohols and TosMIC Mediated by Iodine in DMSO

Naresh Pogaku; Palakodety Radha Krishna; Y. Lakshmi Prapurna

doi:10.1055/s-0037-1610229

Synlett, Table of Contents

Synlett 2018; 29(15): 2039-2042
DOI: 10.1055/s-0037-1610229

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An Efficient Direct Access to Carbamates from Alcohols and TosMIC Mediated by Iodine in DMSO

Naresh Pogaku

^aD-207, Discovery Laboratory, Organic and Biomolecular Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, India CSIR-IICT communication number: IICT/Pubs./2018/234

^bAcademy of Scientific and Innovative Research (AcSIR), New Delhi 110025, India

,

Palakodety Radha Krishna

^aD-207, Discovery Laboratory, Organic and Biomolecular Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, India CSIR-IICT communication number: IICT/Pubs./2018/234

,

Y. Lakshmi Prapurna*

^aD-207, Discovery Laboratory, Organic and Biomolecular Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, India CSIR-IICT communication number: IICT/Pubs./2018/234

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Abstract

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Abstract

A new approach for the synthesis of carbamates from alcohols and TosMIC promoted by iodine/DMSO system is reported. This method offers a one-step, direct and practical strategy for the rapid construction of carbamates under mild conditions. The reaction proceeds via sequential oxidation of isocyanide to isocyanate and nucleophilic addition of alcohols to isocyanate to afford the carbamates in high yields.

Key words

alcohols - TosMIC - carbamate - iodine - DMSO - isocyanate

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References

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16 General Experimental Procedure (Scheme 2, 3a) A mixture of alcohol 1 (0.032 g, 1.0 mmol), TosMIC (2, 0.19 g, 1.0 mmol), and iodine (0.15 g, 0.6 mmol) was stirred in DMSO (2 mL) at room temperature for 15–20 min. After the reaction was complete, the mixture was quenched with a cold saturated aqueous Na₂S₂O₃(2 × 20 mL) solution. Then the solution was extracted with EtOAc (2 × 20 mL). The combined organic layers were dried with anhydrous Na₂SO₄, and the solvent was removed under reduced pressure. The resulting crude product was purified by flash column chromatography on silica gel (eluent: petroleum ether/ethyl acetate, 10:3) to afford 3a (0.22 g, 93% yield). Methyl (Tosylmethyl)carbamate (3a) The general procedure was followed. White solid, mp 142–144 °C. Yield 93% (0.22 g). ¹H NMR (300 MHz, CDCl₃): δ = 7.80 (d, J = 8.2 Hz, 2 H), 7.36 (d, J = 8.0 Hz, 2 H), 5.78 (s, 1 H), 4.56 (d, J = 6.9 Hz, 2 H), 3.57 (s, 3 H), 2.45 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 155.7, 145.4, 133.7, 129.9, 128.9, 62.5, 52.9, 21.7. ESI-MS: 266 [M + Na]⁺. HRMS: m/z calcd for C₁₀H₁₃O₄NNaS [M + Na]⁺: 266.0457; found: 266.0464.

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