Dibromobis(triphenylphosphine)palladium(II)1

PdBr2(PPh3)2
(cis)

[25044-96-9]  · C36H30Br2P2Pd  · Dibromobis(triphenylphosphine)palladium(II)  · (MW 790.81) (trans)

[22180-53-6]

(catalyst for carbonylation of aromatic and vinylic bromides;1-5 arylation of allylic alcohols;6 silylation7 and stannation8 of aromatic bromides)

Physical Data: mp 230-250 °C (dec).

Solubility: sol acetonitrile, DMF, halogenated solvents.

Preparative Method: from commercially available PdCl2(PPh3)2.1b,1c

Handling, Storage, and Precautions: hygroscopic, air sensitive in solution.

Carbonylation.

PdBr2(PPh3)2 (1) is a catalyst that has been used for the carbonylation of aromatic bromides to give carboxylic acids.2 Use of this reagent in a synthesis of anthranilic acids is shown in eq 1.

Aromatic and vinyl bromides have been carbonylated in the presence of amines to give amides (eq 2).3

Carboxylic acid esters are formed from carbonylation of aromatic and vinylic bromides and iodides in the presence of an amine and an alcohol (eq 3).4

Aryl halides and vinyl halides react with carbon monoxide and hydrogen in the presence of amines and (1) to yield aldehydes (eq 4).5

Arylation.

The title reagent has been used to couple aromatic halides with allylic alcohols (eq 5).6 This process is formally equivalent to a conjugate addition between the halide and an unsaturated ketone.

Silylation.

PdBr2(PPh3)2 will catalyze the silylation of aromatic and alkyl bromides with disilanes (eq 6).7

Stannation.

The title reagent has been used to prepare organostannanes from functionalized aromatic bromides and distannanes (eq 7).8 The reaction is especially useful where normal Grignard or organolithium reagents cannot be used.


1. (a) Heck, R. F. Palladium Reagents in Organic Syntheses; Academic: London, 1987. (b) Hartley, F. R. The Chemistry of Platinum and Palladium; Applied Science: London, 1973; p 458. (c) Stille, J. K.; Lan, K. S. Y. JACS 1976, 98, 5841.
2. Valentine, D.; Tilley, J. W.; LeMahieu, R. A. JOC 1981, 46, 4614.
3. Schoenberg, A.; Heck, R. F. JOC 1974, 39, 3327.
4. (a) Schoenberg, A.; Bartoletti, I.; Heck, R. F. JOC 1974, 39, 3318. (b) Kasahara, A.; Izumi, T.; Ogata, H.; Gotou, T.; Kohei, K. Yamagata Daigaku Kiyo, Kogaku 1988, 20, 141 (CA 1981, 114, 246 962c).
5. (a) Schoenberg, A.; Heck, R. F. JACS 1974, 96, 7761. (b) Kasahara, A.; Izumi, T.; Yanai, H. CI(L) 1983, 898.
6. Melpolder, J. B.; Heck, R. F. JOC 1976, 41, 265.
7. Eaborn, C.; Griffiths, R. W.; Pidcock, A. JOM 1982, 225, 331.
8. Azizian, H.; Eaborn, C.; Pidcock, A. JOM 1981, 215, 49.

Anthony Fulford

Johnson Matthey, Royston, UK



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