Chemistry: A European Journal 2009-07-27

Solvent-enhanced diastereo- and regioselectivity in the Pd(II)-catalyzed synthesis of six- and eight-membered heterocycles via cis-aminopalladation.

Arpád Balázs, Anasztázia Hetényi, Zsolt Szakonyi, Reijo Sillanpää, Ferenc Fülöp

Index: Chemistry 15(30) , 7376-81, (2009)

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Abstract

The Pd(II)-catalyzed intramolecular oxidative cyclization of tosyl-protected cis- and trans-N-allyl-2-aminocyclohexanecarboxamides was examined, and efficient syntheses of cyclohexane-fused pyrimidin-4-ones and 1,5-diazocin-6-ones were developed. In the course of the research, a marked solvent effect was observed on both the regio- and diastereoselectivity. Additionally, a novel Pd(II)-mediated domino oxidation, oxidative amination reaction was discovered. Our experimental and theoretical findings suggest that the reactions proceed via a cis-aminopalladation mechanism.