Tetrakis(triethyl phosphite)nickel(0)

[(EtO)3P]4Ni

[14839-39-5]  · C24H60NiO12P4  · Tetrakis(triethyl phosphite)nickel(0)  · (MW 723.41)

(catalyst for allylic alkylation;1 cycloadditions;2 alkene isomerization;3 aldol reaction4)

Physical Data: mp 108 °C; white crystals.

Solubility: sol THF, toluene.

Preparative Methods: easily synthesized by the reaction of Triethyl Phosphite, Nickel(II) Chloride, and Et2NH.5

Handling, Storage, and Precautions: is a cancer suspect agent; air sensitive; reacts with halogenated solvents; should be handled using Schlenk or glovebox techniques.

Allylic Alkylation.

Alkylation of allylic carbonates by 1,3-dicarbonyl compounds under neutral conditions is catalyzed by [(EtO)3P]4Ni (eq 1).1 Alkenyl allyl carbonates undergo an intramolecular decarbonylative allylation with [(EtO)3P]4Ni (eq 2).6

Cycloaddition Reactions.

The cycloaddition of trimethylenemethane intermediates to imines is catalyzed by [(EtO)3P]4Ni to form 4-methylenepyrrolidines (eq 3).2

Alkene Isomerization.

[(EtO)3P]4Ni catalyzes the isomerization of 1-pentene to a mixture of cis- and trans-2-pentene (eq 4).3 At 35 °C, an equilibrium mixture (3:1:1) of trans-2-pentene, cis-2-pentene, and 1-pentene is formed.

Aldol Reaction.

The reaction of aldehydes with b-keto allyl esters is catalyzed by [(EtO)3P]4Ni to form b-hydroxy ketones (eq 5).4


1. Minami, I.; Shimizu, I.; Tsuji, J. JOM 1985, 296, 269.
2. Jones, M. D.; Kemmitt, R. D. W. CC 1986, 1201.
3. Bingham, D.; Webster, D. E.; Wells, P. B. JCS(D) 1972, 1928.
4. Nokami, J.; Konishi, H.; Matsuura, H. CL 1991, 2023.
5. Meier, M.; Basolo, F. Inorg. Synth. 1971, 13, 112.
6. Tsuji, J.; Minami, I.; Shimizu, I. CL 1984, 1721.

Gregory T. Whiteker

Union Carbide Corporation, South Charleston, WV, USA



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