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Synthesis of spirocyclic orthoesters by ‘anomalous’ rhodium(II)-catalysed intramolecular C–H insertions

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Abstract

A tetrahydropyranyl acetal bearing a proximal phenyl diazoketone substituent underwent Rh(II)-catalysed C–H insertion via an ‘anomalous’ C–O bond-forming, rather than C–C bond-forming, transformation, giving spirocyclic orthoesters. Density functional theory calculations with M06 show that the formation of these anomalous products involves hydride transfer to the rhodium carbene, giving an intermediate zwitterion which undergoes C–O bond formation in preference to C–C bond formation.

Graphical abstract: Synthesis of spirocyclic orthoesters by ‘anomalous’ rhodium(ii)-catalysed intramolecular C–H insertions

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Publication details

The article was received on 25 Aug 2017, accepted on 05 Dec 2017 and first published on 05 Dec 2017


Article type: Paper
DOI: 10.1039/C7OB02123B
Citation: Org. Biomol. Chem., 2018, Advance Article
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    Synthesis of spirocyclic orthoesters by ‘anomalous’ rhodium(II)-catalysed intramolecular C–H insertions

    F. J. Lombard, R. J. Lepage, B. D. Schwartz, R. C. Johnston, P. C. Healy, E. H. Krenske and M. J. Coster, Org. Biomol. Chem., 2018, Advance Article , DOI: 10.1039/C7OB02123B

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