Heptanal reductive allylation

In this case an active dendritic Pd°-species could be generated by hydrazine reduction and subsequently used in a DMF/heptane mixture at 75 °C for the stereoselective allylic amination. After completion of the reaction and cooling to room temperature, the catalysts can be recovered by simple phase separation. 

Pd/C also catalyzes the PTC reduction of aryl and heteroaryl halides with sodium formate [52]. The reductive dehalogenation of allyl and benzyl halides with HCOOK can be carried out in a heptane/water system in the presence of water-soluble complexes of type PdCl2(sulfonated phosphine)2 and a PT agent... 

Though the polyether phosphine is capable of acting as a normal PTC [14], this result indicates that the hydrophilic complex transports the allyl acetate from the heptane phase into the aqueous phase and catalyzes the reduction to propene with sodium formate in the aqueous phase [4] (see Scheme 1). 

A counter phase transfer catalysis effect was observed in reduction of allyl chloride with sodium formate in water/n-heptane systems with water soluble palladium(II) catalysts having phosphine ligands with polyether chains [274] it was demonstrated that the catalyst transported the substrate to the aqueous phase where it reacted with the formate. 

The reduction of allylic halides or acetates, as well as benzyl halides, can be achieved by the Pd-catalyzed reaction with formate ions in the biphasic system of toluene-water or heptane-water in the presence of hydrophilic phosphine ligands TPPMS, sodium 3-(diphenylphosphino)benzoate, and PEG-modilied trialkylphosphine. The process is accelerated by the addition of PEGJ ... 

Reaction of allyl halides with the iron powders is rapid and exothermic and leads to near quantitative yields of the self-coupled product 1,5-hexadiene. Similarly, reaction of benzyl chloride with the iron powders at room temperature yields bibenzyl in 60-70% yields along with 20-25% of toluene. In contrast, reaction of aryl halides with the iron powders leads to reductive cleavage rather than self-coupling. Similarly, reaction of 1-bromoheptane with the iron powder in THF for 3h at room temperature produced 35% heptane and no... 

The concept of CPTC has been applied in a large number of catalytic reactions such as reduction of allyl chlorides with HCOONa, carbonylation of aryl and allyl halides, allylation of aldehydes, cyanation of aryl halides etc. For example, Okano et al. reduced l-chloro-2-nonene to afford 1-nonene and 2-nonene (Equation 17) with selectivities of 82% and 17%, respectively using palladium catalysts modified with the water soluble polyether phosphine 76 (Table 4 n=0, x=l, m=3, R=Me) in an heptane/H20 (8/2) two phase system according to CPTC concept. 

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