Regioselective synthesis of aniline-derived 1,3- and Ci-symmetric 1,4-diols from trans-1,4-cyclohexadiene dioxide.
trans-Diepoxide 1 is well-known to react with aliphatic amines and the azide ion to give exclusively the 1,3-diol products. However, we observed that by judicious choice of conditions, reaction with anilines can give predominantly the 1,3-diol (3) or the heretofore rarely seen C(i)-symmetric 1,4-diol (4). Synthesis of an unsymmetrical 1,4-diol from two different anilines is also demonstrated. These studies demonstrate that an intramolecular anilino-NH hydrogen bond donor can direct Fürst-Plattner epoxide opening.
Monceaux
Christopher J
CJ
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, USA.
Carlier
Paul R
PR
D000438:Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D000588:Amines / Q000737:chemistry; D000814:Aniline Compounds / Q000737:chemistry*; D002384:Catalysis; D003510:Cyclohexanes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D006860:Hydrogen Bonding; D015394:Molecular Structure; D013237:Stereoisomerism
C547262:1,2,4,5-diepoxycyclohexane; D000438:Alcohols; D000588:Amines; D000814:Aniline Compounds; D003510:Cyclohexanes; D004852:Epoxy Compounds; C023650:aniline