title: RhII-Catalyzed β-C(sp2)-H Alkylation of Enol Ethers, Enamides and Enecarbamates with α-Diazo Dicarbonyl Compounds.
abstract: A RhII-catalyzed method for intermolecular alkylation of the β-C(sp2)-H bond of enol ethers, enamides, and enecarbamates with α-diazo-1,3-dicarbonyl compounds is reported. The products are formed in up to 99 % yield and can be readily derivatized under a variety of conditions. By utilizing a combination of experimental and computational studies, the presumptive addition-elimination reaction mechanism was investigated and found to proceed under thermodynamic control at higher temperature. The acquired fundamental knowledge was translated into a strategic reaction design and yielded the first example of the β-C-H functionalizations of acyclic enol ethers using α-diazo-1,3-dicarbonyl compounds.
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia, 30332, USA.
authors.forename: Brett D
authors.initials: BD
authors.lastname: McLarney
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia, 30332, USA.
authors.forename: Marchello A
authors.initials: MA
authors.lastname: Cavitt
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia, 30332, USA.
authors.forename: Theodore M
authors.initials: TM
authors.lastname: Donnell
authors.affiliation: Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia, 30322, USA.
authors.forename: Djamaladdin G
authors.initials: DG
authors.lastname: Musaev
authors.affiliation: School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia, 30332, USA.|Petit Institute of Bioengineering and Bioscience, Georgia Institute of Technology, Atlanta, Georgia, 30332, USA.
authors.forename: Stefan
authors.identifier: http://orcid.org/0000-0001-5998-6167
authors.initials: S
authors.lastname: France
keywords: C−H activation; addition/elimination; alkylation; diazo compounds; rhodium