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Dipolar addition to cyclic vinyl sulfones leading to dual conformation tricycles.

ABSTRACT: Dipolar addition of cyclic azomethine imines with cyclic vinyl sulfones gave rise to functionalized tricycles that exhibited fluxional behavior in solution at room temperature. The scope of the synthetic methodology was explored, and the origin of the fluxional behavior was probed by NMR methods together with DFT calculations. This behavior was ultimately attributed to stereochemical inversion at one of two nitrogen centers embedded in the tricyclic framework. Two tetracycles were also synthesized, and the degree of signal-broadening in the NMR spectra was found to depend on the presence of substitution next to the inverting nitrogen center.

SUBMITTER: Wong SS

PROVIDER: S-EPMC3740686 | biostudies-literature | 2013

REPOSITORIES: biostudies-literature

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Dipolar addition to cyclic vinyl sulfones leading to dual conformation tricycles.

Wong Steven S Y SS Brant Michael G MG Barr Christopher C Oliver Allen G AG Wulff Jeremy E JE

Beilstein journal of organic chemistry 20130715

Dipolar addition of cyclic azomethine imines with cyclic vinyl sulfones gave rise to functionalized tricycles that exhibited fluxional behavior in solution at room temperature. The scope of the synthetic methodology was explored, and the origin of the fluxional behavior was probed by NMR methods together with DFT calculations. This behavior was ultimately attributed to stereochemical inversion at one of two nitrogen centers embedded in the tricyclic framework. Two tetracycles were also synthesiz ...[more]

PMID: 23946837

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