Primary tetrakis palladium

Allylic acetates of either geranyl acetate or neryl acetate reacted with the sodium salt of methyl phenylsulfonyl acetate in the presence of tetrakis(triphenylphosphine palladium) affording the corresponding olefin, with a retained geometry at the primary carbon... 

Primary allylic amines. Unlike the benzyl group, the 4,4 -dimethoxybenz-hydryl (DMB) group is removed by mild acid treatment. Because of this property, it was chosen as the protecting group in a recent synthesis of primary allylic amines by Trost and Keinan. A typical example is shown in equation (I). Treatment of an allylic acetate (2) with 1 in the presence of tetrakis(triphenylphosphine)palladium(0) results in the (E)-allylic amine 3 in 81% yield. The protecting group is removed readily to give 4 in 82% yield. 

The addition of malonates and related C-H acidic compounds to activated vinylcyclopropanes has also been performed with tetrakis(triphenylphosphane)palladium(0) rather than sodium alkoxide. ° The primary products 12 arising from the 1,7-addition can react with a second molecule of the vinylcyclopropane derivative in the same fashion to give afford 1 2 adducts 13. 

Furthermore, homobimetallic dimers derived from phosphinous acids [134] or phosphine chlorides [239], palladium nanoparticles stabilized by wBu4NBr [142], as well as the catalyst derived from [Pd(C3H5)Cl]2 as well as the tetraphosphine ligand Tedicyp (l,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane) [240] are also systems with high catalytic activity that enable the cross-coupling of primary alkylzincs and aryl bromides or iodides with good generality. 

Phenylsulphonyl)nitromethane is C-alkylated preferentially by benzyl halides, primary alkyl iodides, and allylic acetates, the latter in the presence of catalytic tetrakis(triphenylphosphine)palladium, providing secondary a-nitrosul-phones (cf. Vol. 5, p. 197). The synthetic utility of this process, other than for the preparation of a-nitrosulphones themselves, has been enhanced by the development of efficient desulphonation processes, " thus providing an overall synthesis of nitroalkanes. Nitroalkanes are also the products of the replacement of tertiary nitro groups by nitromethyl via sodio nitromethane. ... 

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