[32002-24-7] · C9H16O4 · Ethyl 3,3-Diethoxyacrylate · (MW 188.25)
(used in cycloaddition reactions with cyclopentenones, 1-aza-1,3-butadienes, and alkynylalkoxycarbene metal complexes to give carbocyclic and heterocyclic compounds; undergoes [3,3]-sigmatropic rearrangement with allylic alcohols to give substituted allylmalonates.)
Physical Data: bp 122-123 °C/10 mmHg; n
Solubility: sol organic solvents.
Handling, Storage, and Precautions: keep away from moisture. Handle in a fume hood.
Ethyl 3,3-diethoxyacrylate (1) is prepared1 from Ethyl Cyanoacetate by the Pinner reaction.2 It has been used in a variety of cycloaddition reactions. Head-to-tail regioselectivity in the [p2 + p2] photocycloaddition of (1) with cyclopentenones (2) to give the bicyclo[3.2.0]heptanones (3) was significantly better than that observed with methyl b-acetoxyacrylate. Treatment of the cycloaddition products (3) with Sodium Borohydride followed by p-Toluenesulfonic Acid gave the lactones (4).3
Cycloaddition of the alkynylalkoxycarbene metal complexes (5) with (1) provided (8), via (7) and, presumably, (6). Oxidation of (8) with Dimethyl Sulfoxide gave the 6-ethoxy-2H-pyrones (9).4
Reaction of (1) and the 1-aza-1,3-butadiene (10) in a [4 + 2] cycloaddition reaction at 13 kbar (1300 MPa) provided (11), which was converted to the pyridine (12) by treatment with 1,8-Diazabicyclo[5.4.0]undec-7-ene.5
Raucher reported that the [3,3]-sigmatropic rearrangement of (1) with allylic alcohols (13) using a catalytic amount of 2,4,6-Trimethylbenzoic Acid provides a convenient method for the regiospecific synthesis of substituted allylmalonate esters (15).6 The alcohols examined were (16)-(22).
Trost reported that reaction of (1) and (23) with a catalytic amount of Pyridinium p-Toluenesulfonate at room temperature gave (24), an intermediate in a total synthesis of (-)-aspochalasin B.7
University of Washington, Seattle, WA, USA