Cyclopropanation of (E)-Dehydroaspartic Acid Esters with Furan Derivatives: The Synthesis of Highly Functionalized α-2,3-Methanoamino Acid Esters

Abstract

Highly functionalized α-2,3-methanoamino acid esters were prepared by the cyclopropanation of dehydroaspartic acid esters with 2-methoxyfuran or 2-siloxyfuran derivatives. These reactions proceed smoothly in the absence of any catalysts, bases, additives, or solvents.

Key words

cyclopropanation - α-2,3-methanoamino acids - furans - dehydroaspartic acid ester

• References and Notes

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• 8 General Procedure for the Cyclopropanation Reaction (Synthesis of 13a) A mixture of 10 (36.4 mg, 0.120 mmol) and 12a (288 mg, 1.20 mmol) was heated to 120 °C in a sealed tube reactor for 21 h. After cooling the mixture to r.t., the crude mixture was subjected to silica gel column chromatography to give 13a (40.4 mg, 62%) as a yellow oil. ¹H NMR (300 MHz, CDCl₃): δ = 7.83 (m, 2 H), 7.73 (m, 2 H), 6.29 (dd, J = 11.4, 8.7 Hz, 1 H), 6.08 (d, J = 11.4 Hz, 1 H), 4.30 (t, J = 8.7 Hz, 1 H), 4.09 (q, J = 7.2 Hz, 2 H), 3.69 (s, 3 H), 3.11 (d, J = 8.7 Hz, 1 H), 1.31 (m, 3 H), 1.20 (t, J = 7.2 Hz, 3 H), 1.07 (d, J = 7.2 Hz, 18 H). ¹³C NMR (75 MHz, CDCl₃): δ = 167.4, 167.0, 165.2, 138.5, 134.2, 134.1, 126.2, 123.6, 123.5, 61.5, 53.5, 42.6, 34.0, 32.8, 17.7, 13.9, 11.9. FTIR (neat): 2951, 2871, 1730, 1398, 1273, 1202, 721 cm^–1. HRMS–FAB: m/z calcd for C₂₈H₃₈NO₈Si [M + H]⁺: 544.2367; found: 544.2369.