Palladium-catalyzed reactions of aryl bromides and chlorides with two common stabilized carbanions-enolates of dialkyl malonates and alkyl cyanoesters-are reported. An exploration of the scope of these reactions was conducted, and the processes were shown to occur in a general fashion. Using P(t-Bu)(3) (1), the pentaphenylferrocenyl ligand (Ph(5)C(5))Fe(C(5)H(4))P(t-Bu)(2) (2), or the adamantyl ligand (1-Ad)P(t-Bu)(2) (3), reactions of electron-poor and electron-rich, sterically hindered and unhindered aryl bromides and chlorides were shown to react with diethyl malonate, di-tert-butyl malonate, diethyl fluoromalonate, ethyl cyanoacetate, and ethyl phenylcyanoacetate. Although alkyl malonates and ethyl alkylcyanoacetates did not react with aryl halides using these catalysts, the same products were formed conveniently in one pot from diethylmalonate by cross-coupling of an aryl halide in the presence of excess base and subsequent alkylation.

Supporting Information General Methods. 1 H and 13 C NMR spectra were recorded on a Bruker DPX 400 MHz Spectrometer, General Electric QE 300 MHz spectrometer, or a General Electric Omega 500 spectrometer with tetramethylsilane or residual protiated solvent used as a reference and coupling constants reported in Hertz (Hz). Elemental analyses were performed by Robertson Microlabs, Inc., Madison, NJ. Chromatographic purifications were performed by flash chromatography 1 using silica gel (200-400 mesh) from Natland International Corporation. Yields for final products in Table 1 refer to isolated yields and are the average of at least two runs. Spectroscopic data and combustion analyses are reported for new compounds (Entry 11,

Palladium-Catalyzed Arylation of Malonates and Cyanoesters UsingSterically Hindered Trialkyl-and Ferrocenyldialkylphosphine Ligands.-The enolates of diethyl and di-tert-butyl malonates, and of ethyl cyanoacetates are arylated by a wide variety of aryl bromides or chlorides using catalysts derived from Pd(dba) 2 or [PdCl(allyl)] 2 and sterically demanding phosphines. By varying the base, the solvent and the catalyst, the yields can be optimized. -(BEARE, NEIL A.; HARTWIG, JOHN F.; J. Org. Chem. 67 (2002) 2, 541-555; Dep. Chem., Yale Univ., New Haven, CT 06520, USA; EN)

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