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Nitrone Cycloadditions of 1,2-Cyclohexadiene.

ABSTRACT: We report the first 1,3-dipolar cycloadditions of 1,2-cyclohexadiene, a rarely exploited strained allene. 1,2-Cyclohexadiene is generated in situ under mild conditions and trapped with nitrones to give isoxazolidine products in synthetically useful yields. The reactions occur regioselectively and exhibit a notable endo preference, thus resulting in the controlled formation of two new bonds and two stereogenic centers. DFT calculations of stepwise and concerted reaction pathways are used to rationalize the observed selectivities. Moreover, the strategic manipulation of nitrone cycloadducts demonstrates the utility of this methodology for the assembly of compounds bearing multiple heterocyclic units. These studies showcase the exploitation of a traditionally avoided reactive intermediate in chemical synthesis.

SUBMITTER: Barber JS

PROVIDER: S-EPMC4899974 | biostudies-other | 2016 Mar

REPOSITORIES: biostudies-other

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Nitrone Cycloadditions of 1,2-Cyclohexadiene.

Barber Joyann S JS Styduhar Evan D ED Pham Hung V HV McMahon Travis C TC Houk K N KN Garg Neil K NK

Journal of the American Chemical Society 20160218 8

We report the first 1,3-dipolar cycloadditions of 1,2-cyclohexadiene, a rarely exploited strained allene. 1,2-Cyclohexadiene is generated in situ under mild conditions and trapped with nitrones to give isoxazolidine products in synthetically useful yields. The reactions occur regioselectively and exhibit a notable endo preference, thus resulting in the controlled formation of two new bonds and two stereogenic centers. DFT calculations of stepwise and concerted reaction pathways are used to ratio ...[more]

PMID: 26854652

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