Synthesis of complex allylic esters via C-H oxidation vs C-C bond formation.
A highly general, predictably selective C-H oxidation method for the direct, catalytic synthesis of complex allylic esters is introduced. This Pd(II)/sulfoxide-catalyzed method allows a wide range of complex aryl and alkyl carboxylic acids to couple directly with terminal olefins to furnish (E)-allylic esters in synthetically useful yields and selectivities (16 examples, E/Z >or= 10:1) and without the use of stoichiometric coupling reagents or unstable intermediates. Strategic advantages of constructing allylic esters via C-H oxidation vs C-C bond-forming methods are evaluated and discussed in four "case studies".
Vermeulen
Nicolaas A
NA
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
Delcamp
Jared H
JH
White
M Christina
MC
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry; D002384:Catalysis; D004952:Esters; D006859:Hydrogen / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013379:Substrate Specificity
D000475:Alkenes; D002264:Carboxylic Acids; D004952:Esters; D002244:Carbon; D006859:Hydrogen