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Issue 39, 2013
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Diastereotopic group selectivity and chemoselectivity of alkylidene carbene reactions on 8-oxabicyclo[3.2.1]oct-6-ene ring systems

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Abstract

α-Hydroxyalkylidene carbenes, generated from thermolysis of α,β-epoxy-N-aziridinylimines, undergo diastereotopic group selective 1,5 C–H insertion reactions on 2,4-dimethyl-8-oxabicyclo[3.2.1]oct-6-ene ring systems. Protection of a tertiary alcohol at C-3 of the bridged oxabicycle as a trimethylsilyl ether reverses the sense of diastereoselectivity. 1,5 C–H insertion into a methine adjacent to an OBn group, 1,5 O–R insertion into a tertiary alcohol (R = H) or silylether (R = TMS) at C-3 to form spirocyclic dihydrofurans, 1,2-rearrangement to an alkyne and fragmentation to a ketone are competing major pathways for 2-benzyloxy-substituted 8-oxabicyclo[3.2.1]oct-6-ene systems. Dihydrofuran formation is shown to be a result of substitution on the oxabicyclic ring system through comparison with other methods of alkylidene carbene formation.

Graphical abstract: Diastereotopic group selectivity and chemoselectivity of alkylidene carbene reactions on 8-oxabicyclo[3.2.1]oct-6-ene ring systems

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Publication details

The article was received on 06 Jul 2013, accepted on 29 Aug 2013 and first published on 30 Aug 2013


Article type: Paper
DOI: 10.1039/C3OB41390J
Citation: Org. Biomol. Chem., 2013,11, 6856-6862
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    Diastereotopic group selectivity and chemoselectivity of alkylidene carbene reactions on 8-oxabicyclo[3.2.1]oct-6-ene ring systems

    K. R. Munro, L. Male, N. Spencer and R. S. Grainger, Org. Biomol. Chem., 2013, 11, 6856
    DOI: 10.1039/C3OB41390J

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