Copper(I) Cyanoacetate


[51249-59-3]  · C3H2CuNO2  · Copper(I) Cyanoacetate  · (MW 147.60)

(agent generating cyanomethylcopper(I);1 transcarboxylating agent for epoxides2 and ketones5)

Solubility: insol ordinary organic solvents; sol organic solvents in the presence of tertiary phosphine ligands.

Preparative Methods: acidolysis of Copper(I) t-Butoxide;1 carboxylate exchange reaction between CuI n-butyrate and Cyanoacetic Acid.3

Handling, Storage, and Precautions: oxygen- and moisture-sensitive; preparation and reaction should be conducted under rigorously oxygen-free and anhydrous conditions.

Generation of Cyanomethylcopper(I).

CuI cyanoacetate decarboxylates in DMF at 50 °C to generate cyanomethylcopper(I) (eq 1).1 Preparation of cyanomethylcopper(I) using decarboxylation of CuI cyanoacetate is characterized by the absence of lithium halide, in contrast to its preparation using the metathesis reaction between CuI halide and Isocyanomethyllithium. Cyanomethylcopper(I) acts as a cyanomethylating agent of organic halides (eq 1). CuII cyanoacetate decarboxylates similarly to produce cyanomethylcopper(I) with concomitant formation of succinonitrile (eq 2).1 Synthetic use of Cyanomethylcopper is described in the corresponding entry.

Transcarboxylation of Epoxides and Ketones.

CuI cyanoacetate acts as a CO2 carrier, transferring its CO2 moiety to propene oxide to afford propene carbonate in high yield (eq 3).2 CuI cyanoacetate and cyanomethylcopper(I) catalyze the reaction of propene oxide with CO2 to give propene carbonate.

CuI cyanoacetate-catalyzed carboxylation of trans-1,2-dideuteroethylene oxide proceeds stereospecifically with retention of configuration, while the nickel(0) catalyst effects nonstereospecific reaction (eq 4).4

In the presence of Tri-n-butylphosphine ligand, the decarboxylation of CuI cyanoacetate in DMF is highly suppressed, resulting in reversible decarboxylation (eq 5).5 The CuI cyanoacetate-tri-n-butylphosphine complex acts as a reversible CO2 carrier to transfer its CO2 component to cyclohexanone in good yield (eq 6).5

1. Tsuda, T.; Nakatsuka, T.; Hirayama, T.; Saegusa, T. CC 1974, 557.
2. Tsuda, T.; Chujo, Y.; Saegusa, T. CC 1976, 415.
3. Edwards, D. A.; Richards, R. JCS(D) 1973, 2463.
4. Bäckvall, J.-E.; Karlsson, O. TL 1980, 21, 4985.
5. Tsuda, T.; Chujo, Y.; Saegusa, T. JACS 1978, 100, 630.

Tetsuo Tsuda

Kyoto University, Japan

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