(3+2)-Cycloaddition of Donor–Acceptor Cyclopropanes with Thiocyanate: A Facile and Efficient Synthesis of 2-Amino-4,5-dihydrothiophenes

Abstract

An easy and efficient route to obtain 2-amino-4,5-dihydrothiophenes is presented. A formal (3+2)-cycloaddition of donor–acceptor cyclopropanes and ammonium thiocyanate catalyzed by Yb(OTf)₃ delivers the desired products in good to excellent yields. A broad range of functional groups is tolerated during this process.

Key words

D–A cyclopropanes - dihydrothiophenes - Lewis acid catalysis - thiocyanate - cycloaddition

Publication History

Received: 21 January 2021

Accepted after revision: 07 February 2021

Accepted Manuscript online:
07 February 2021

Article published online:
05 March 2021

• References and Notes

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• 22 General Procedure for the Preparation of 2-Amino-dihydrothiophenes (3) Cyclopropane diester 1 (100 μmol, 1.00 equiv), ammonium thiocyanate 2 (200 μmol, 2.00 equiv), and ytterbium triflate (19 mg, 30.0 μmol, 0.30 equiv were dissolved in THF (1 mL). The solution was stirred at 75 °C for 12 h. The solvent was removed, and the residue was purified by flash column chromatography. Methyl 2-Amino-5-(4-chlorophenyl)-4,5-dihydrothiophene-3-carboxylate (3c) Colorless solid; yield 50%; mp 146 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.36–7.33 (m, 2 H), 7.31–7.27 (m, 2 H), 6.08 (s, 2 H), 4.79 (dd, J = 8.5, 6.9 Hz, 1 H), 3.69 (s, 3 H), 3.40 (dd, J = 14.3, 8.5 Hz, 1 H), 3.10 (dd, J = 14.2, 6.9 Hz, 1 H). ¹³C NMR (156 MHz, CDCl₃): δ = 166.5, 161.9, 140.2, 133.5, 128.8, 128.4, 90.4, 50.5, 50.4, 41.4. HRMS (ESI): m/z calcd for C₁₂H₁₂ClNO₂S [M + Na]: 292.0175; found: 292.0172. Methyl 2-Amino-5-(p-tolyl)-4,5-dihydrothiophene-3-carboxylate (3e) Colorless solid; yield 68%; mp 100 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.30 (d, J = 8.2 Hz, 2 H), 7.15–7.10 (m, 2 H), 6.06 (s, 2 H), 4.83 (t, J = 8.0 Hz, 1 H), 3.68 (s, 3 H), 3.37 (dd, J = 14.2, 8.5 Hz, 1 H), 3.14 (dd, J = 14.2, 7.6 Hz, 1 H), 2.33 (s, 3 H). ¹³C NMR (156 MHz, CDCl₃): δ = 166.6, 162.3, 138.4, 137.5, 129.3, 127.0, 90.8, 51.3, 50.4, 41.4, 21.0. HRMS (ESI): m/z calcd for C₁₃H₁₅NO₂S [M + Na]: 272.0721; found: 272.0717.