Ethyl 3,3-Diethoxyacrylate

[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; n25D 1.4597.1

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

Related Reagents.

Diethyl Ethoxymethylenemalonate; Ethyl 3,3-Diethoxypropanoate; Ethyl 3-Ethoxyacrylate; Ketene Diethyl Acetal; Methylketene Dimethyl Acetal.

1. (a) Glickman, S. A.; Cope, A. C. JACS 1945, 67, 1017. (b) McElvain, S. M.; Schroeder, J. P. JACS 1949, 71, 40.
2. DeWolfe, R. H. S 1974, 153.
3. Van Audenhove, M.; Termont, D.; De Keukeleire, D.; Vandewalle, M. TL 1978, 2057.
4. Camps, F.; Moreto, J. M.; Ricart, S.; Vinas, J. M.; Molins, E.; Miravitilles, C. CC 1989, 1560.
5. Boger, D. L.; Zhang, M. JOC 1992, 57, 3974.
6. Raucher, S.; Chi, K. W.; Jones, D. S. TL 1985, 26, 6261.
7. Trost, B. M.; Ohmori, M.; Boyd, S. A.; Okawara, H.; Brickner, S. J. JACS 1989, 111, 8281.

Stanley Raucher

University of Washington, Seattle, WA, USA

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