Aldehydes reductive aminations, palladium® acetate

A regio- and stereoselective formation of homoallylic alcohols and amines has been realized by the reaction of easily available allylic acetates 213 and 217 with bispinacolatodiboron 149 in the presence of palladium catalysts followed by the addition of aldehydes/imines (Scheme 36) <2005EJO2539>. The mechanism involves the formation of an 7]3-allyl-Pd complex, which inserts between B-B bond, and subsequent reductive elimination to yield the allyl... 

Various 2-oxo compounds have been subjected to a variety of reactions. Alkylation and acylation result in the formation of 1,3-disubstituted products.Similarly the Mannich reaction with morpholine gives products such as the bis compound 107. Halogenation of the 0x0 compound 108 with bromine in acetic acid," or chlorine in acetic acid, ° or with sulfuryl chloride results in formation of the monohalo derivatives 109. The chlorine atom in 109 (R = Cl) can be removed by hydrogenation over palladium on charcoal. Nitration of the chloro compound 110 with a mixture of nitric and sulfuric acids provides the nitro derivative 111, which may be catalytically reduced to the amino compound 112. If the reduction is carried out in the presence of an aldehyde, the product is a substituted amino derivative (113). Alternatively the amine 112 can be condensed with an aldehyde and the resultant Schiff base reduced to give the product 113. 

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