Solvent-enhanced diastereo- and regioselectivity in the Pd(II)-catalyzed synthesis of six- and eight-membered heterocycles via cis-aminopalladation.
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.
Balázs
Arpád
A
Institute of Pharmaceutical Chemistry, University of Szeged, 6720 Szeged, Eötvös u. 6, Hungary.
Hetényi
Anasztázia
A
Szakonyi
Zsolt
Z
Sillanpää
Reijo
R
Fülöp
Ferenc
F
D000498:Allyl Compounds / Q000737:chemistry*; D000586:Amination; D001392:Azocines / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D003509:Cyclohexanecarboxylic Acids / Q000138:chemical synthesis* / Q000737:chemistry; D003510:Cyclohexanes / Q000138:chemical synthesis* / Q000737:chemistry; D003514:Cyclohexylamines / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D011744:Pyrimidinones / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000138:chemical synthesis*
D000498:Allyl Compounds; D001392:Azocines; D003509:Cyclohexanecarboxylic Acids; D003510:Cyclohexanes; D003514:Cyclohexylamines; D011744:Pyrimidinones; D014753:Vinyl Compounds; C103271:2-aminocyclohexanecarboxylic acid; D010165:Palladium