Diethyl 2-Pentenedioate

(R = Et)

[2049-67-4]  · C9H14O4  · Diethyl 2-Pentenedioate  · (MW 186.21) (E)-(R = Et)

[73178-43-5] (R = Me)

[5164-76-1]  · C7H10O4  · Dimethyl 2-Pentenedioate  · (MW 158.15) (E)-(R = Me)


(effects annulations that involve the reagent's alkenic group,1 and annulations in which the reagent functions as a bis-nucleophile2)

Alternate Name: diethyl glutaconate.

Physical Data: diethyl: bp 236-238 °C, 125 °C/12 mmHg; d 1.053 g cm-3.

Solubility: sol DME, DMSO, MeOH, HOAc.

Form Supplied in: the diethyl ester is more readily available commercially. It is supplied as a liquid (E)/(Z) mixture in 98% purity.

Analysis of Reagent Purity: diethyl: 1H NMR.3

Purification: vacuum distillation.

Annulations Involving the Reagent's Alkenic Bond.

A number of applications of this reagent require the central, alkenic carbon to serve as one point of attachment in annulation processes. Eq 14 demonstrates a straightforward conjugate addition-intramolecular Friedel-Crafts acylation tandem, whereas a conceptually if not mechanistically related electrochemical process is shown in eq 2.5

An additional transformation of this type in which the reagent provides both conjugate addition and nucleophilic reaction sites for ring formation is shown in eq 3.1

Annulations without Reaction at an Alkenic Site.

Processes that append a five-carbon unit derived from the reagent without the attachment of substituents at the reagent's central carbon are also known. In eq 4,6 eq 5,7 and eq 62 the reagent acts as a bis-nucleophile in ring-forming processes.

1. Houwing, H. A.; van Leusen, A. M. JHC 1981, 18, 1127.
2. Rieck, J. A.; Grunwell, J. R. JOC 1980, 45, 3512.
3. The Aldrich Library of NMR Spectra, 2nd ed.; Aldrich Chemical Company: Milwaukee, WI, 1983; p 544B.
4. (a) Kirchlechner, R.; Rogalski, W. TL 1980, 21, 247. See also: (b) Kemp, D. S.; Sidell, M. D.; Shortridge, T. J. JOC 1979, 44, 4473.
5. Shono, T.; Ohmizu, H.; Kawakami, S.; Sugiyama, H. TL 1980, 21, 5029.
6. Jutz, C.; Schweizer, E.; Löbering, H.-G.; Kraatz, A.; Kosbahn, W. CB 1974, 107, 2956.
7. Jackson, D. A.; Lacy, P. H.; Smith, D. C. C. JCS(P1) 1989, 215.

Charles S. Swindell

Bryn Mawr College, PA, USA

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