Effect of additives on chemoselectivity and diastereoselectivity in the catalytic epoxidation of chiral allylic alcohols with hydrogen peroxide and binuclear manganese complexes.
The catalytic oxidations of chiral allylic alcohols 2 by manganese complexes of the cyclic triamine 1,4,7-trimethyl-1,4,7-triazacyclononane (tmtacn) 1 and hydrogen peroxide as oxygen donor in the presence of co-catalyst are investigated to understand the factors that affect the catalyst selectivity. Chemoselectivity and diastereoselectivity of catalyst 1 are significantly affected by the structure of the allylic alcohol and the nature and amount of co-catalyst. More pronounced is the influence of the amount of added molar equivalents of H(2)O(2) (20-110 mol % with respect to the substrate). Our present results reflect the complex redox chemistry of the Mn catalyst 1/H(2)O(2)/co-catalyst system in the early phase of the alkene oxidation.
Kilic
Hamdullah
H
Faculty of Science, Department of Chemistry, Ataturk University, 25240 Erzurum, Turkey. hkilic@atauni.edu.tr
Adam
Waldemar
W
Alsters
Paul L
PL
D001372:Aza Compounds / Q000737:chemistry; D002384:Catalysis; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D020005:Propanols / Q000737:chemistry*; D013237:Stereoisomerism
C499747:1,4,7-trimethyl-1,4,7-triazacyclononane; D001372:Aza Compounds; D004852:Epoxy Compounds; D009942:Organometallic Compounds; D020005:Propanols; C006463:allyl alcohol; D008345:Manganese; D006861:Hydrogen Peroxide