Diazo Esters as Dienophiles in Intramolecular (4 + 2) Cycloadditions: Computational Explorations of Mechanism.

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 inte...

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Bibliographic Details
Published in:	Journal of the American Chemical Society Vol. 139; no. 7; pp. 2766 - 2771
Main Authors:	Abing Duan, Peiyuan Yu, Fang Liu, Huang Qiu, Feng Long Gu, Doyle, Michael P., Houk, K. N.
Format:	Article
Published:	American Chemical Society 2/22/2017
Subjects:	Diazo compounds Ring formation (Chemistry) Diels-Alder reaction Dienophiles Density functional theory
Online Access:	View this record in EBSCOhost

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Summary:	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.