title: Diazo Esters as Dienophiles in Intramolecular (4 + 2) Cycloadditions: Computational Explorations of Mechanism.
abstract: The first experimental examples of Diels-Alder (DA) reactions of diazo compounds as heterodienophiles with dienes have been studied with density functional theory (DFT) using the M06-2X functional. For comparison, the reactivities of diazo esters as dienophiles or 1,3-dipoles with 1,3-dienes in intermolecular model systems have been analyzed by the distortion/interaction model. The 1,3-dipolar cycloaddition is strongly favored for the intermolecular system. The intramolecular example is unique because the tether strongly favors the (4 + 2) cycloaddition.
authors.affiliation: Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education; School of Chemistry and Environment, South China Normal University , Guangzhou 510006, China.|Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Abing
authors.initials: A
authors.lastname: Duan
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Peiyuan
authors.identifier: 0000-0002-4367-6866
authors.initials: P
authors.lastname: Yu
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Fang
authors.initials: F
authors.lastname: Liu
authors.affiliation: Department of Chemistry, The University of Texas at San Antonio , San Antonio, Texas 78249, United States.
authors.forename: Huang
authors.initials: H
authors.lastname: Qiu
authors.affiliation: Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education; School of Chemistry and Environment, South China Normal University , Guangzhou 510006, China.
authors.forename: Feng Long
authors.initials: FL
authors.lastname: Gu
authors.affiliation: Department of Chemistry, The University of Texas at San Antonio , San Antonio, Texas 78249, United States.
authors.forename: Michael P
authors.identifier: 0000-0003-1386-3780
authors.initials: MP
authors.lastname: Doyle
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: K N
authors.identifier: 0000-0002-8387-5261
authors.initials: KN
authors.lastname: Houk