Copper(I) Iodide-Triethyl Phosphite


[51717-23-8]  · C6H15CuIO3P  · Copper(I) Iodide-Triethyl Phosphite  · (MW 356.60)

(promoter for the conjugate addition of alkyllithium and other reagents to a,b-unsaturated ketones and related compounds, regiospecific Ullmann reactions, alkylation of aluminates, and stereoselective synthesis of vinylsilanes)

Physical Data: mp 107-109 °C.1,2

Solubility: sol benzene, cyclohexane, bromoform, acetone, ether, and THF; also sol warm petroleum ether.

Form Supplied in: white crystals (97%).

Preparative Method: the complex is obtained in 88.6% yield by addition of Copper(I) Iodide to a solution of Triethyl Phosphite in benzene; the mixture is stirred and heated until the CuI dissolves; the complex is obtained upon evaporation of the solvent under reduced pressure.2

Purification: recrystallized from petroleum ether.2

Analysis of Reagent Purity: recrystallization and elemental analysis; IR spectrum provided.2

Handling, Storage, and Precautions: irritant; use in a fume hood; mechanical exhaust required; harmful by inhalation, ingestion, or skin absorption; incompatible with strong oxidizing agents; sensitive to air, moisture, and light; store under N2 in a cool dry place.

Copper(I) iodide-triethyl phosphite reacts with acid chlorides in an Arbuzov-type process.2 This complex also promotes alkylation of 1-trimethylsilylvinylaluminates with primary alkyl iodides to produce trisubstituted alkenes (eq 1),3 as well as with 1-trimethylsilylvinylboranes and other alkyl halides.4

Organosamarium species have been generated by in situ transmetalation with copper(I) iodide-triethyl phosphite.5 Although primary alkyl halides are reported to be relatively inert to copper solutions prepared from CuI and triethyl phosphite,6 the complex was found to be effective for the transmetalation of an aryl organolithium which was subsequently utilized in an Ullmann type condensation (eq 2).7

Related Reagents.

Copper(I) Iodide-Tributylphosphine; Copper(I) Iodide-Tributyl Phosphite; Copper(I) Iodide-Triethylphosphine-Lithium Naphthalenide; Copper(I) Iodide-Trimethyl Phosphite.

1. Arbusoff, A. B 1905, 38, 1171.
2. Nishizawa, Y. BCJ 1961, 34, 1170.
3. Ziegler, F. E.; Mikami, K. TL 1984, 131.
4. (a) Uchida, K.; Utimoto, K.; Nozaki, H. JOC 1976, 41, 2941. (b) Uchida, K.; Utimoto, K.; Nozaki, H. T 1977, 33, 2987.
5. Totleben, M. J.; Curran, D. P.; Wipf, P. JOC 1992, 57, 1740.
6. Wehmeyer, R. M.; Rieke, R. D. JOC 1987, 52, 5056.
7. (a) Ziegler, F. E.; Fowler, K. W.; Kanfer, S. JACS 1976, 98, 8282. (b) Ziegler, F. E.; Fowler, K. W.; Sinha, N. D. TL 1978, 2767.

Linda M. Mascavage

Beaver College, Glenside, PA, USA

David R. Dalton

Temple University, Philadelphia, PA, USA

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