Reactions with C, N, O, S and P Nucleophiles

Although arylation or alkenylation of active methylene compounds can be carried out using a Cu catalyst, the reaction is sluggish. However, the arylation of malononitrile (390) or cyanoacetate proceeds smoothly in the presence of a base and Pd catalysts [189], Tetracyanoquinodimethane (392) is prepared by the coupling of / -diiodoben-zene with malononitrile (390) to give 391, followed by oxidation [190], Presence of the cyano group seems to be essential for intermolecular reactions. However, the intramolecular arylation of malonates, / -keto esters and /i-diketones proceeds smoothly [191]. The bromoxazole 393 reacts with phenylsulphonylacetonitrile (394) 

Intermolecular a-arylation of the ketone 399 with o-tolyl bromide (398) gives 400 under selected conditions using f-BuONa or KN(SiMe2)2 as suitable bases, and BINAP or DPPF (XLIX) as a bulky ligand [194], Furthermore, asymmetric arylation of the ketone 402 with the bromide 401 gave 403 with 98% ee efficiently by using chiral BINAP [195]. 

Displacement of aryl and alkenyl iodides with KCN, or aryl triflates with Zn(CN)2 [196] to afford the aryl nitrile 404 is catalyzed by a Pd complex. Similar displacement of aryl chlorides is catalyzed by a Ni complex [197]. 

The N-aryl imines 412 as protected anilines can be prepared by Pd-catalysed arylation of benzophenone imine with aryl halides using DPPF and BINAP as ligands, and aniline derivatives are obtained by deprotection [204a], 

The coupling of chiral amines with aryl bromides proceeds without racemization by proper choice of ligands. Intermolecular animation of a chiral amine proceeds without loss of enantiomeric purity with Pd(0)-(o-Tol)3P. Synthesis of the optically pure indole 415, an intermediate for the synthesis of a potent ACE inhibitor, has been achieved by the Pd-catalyzed amination of 414, which is prepared by the Heck reaction of bromide 413 and Rh-catalyzed aymmetric hydrogenation [205], 

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