Synthesis of spirocyclic orthoesters by ‘anomalous’ rhodium(ii)-catalysed intramolecular C–H insertions
Literature Information
Fanny J. Lombard, Romain J. Lepage, Brett D. Schwartz, Ryne C. Johnston, Peter C. Healy, Elizabeth H. Krenske
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.
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Organic & Biomolecular Chemistry

Organic & Biomolecular Chemistry (OBC) publishes original and high impact research and reviews in organic chemistry. We welcome research that shows new or significantly improved protocols or methodologies in total synthesis, synthetic methodology or physical and theoretical organic chemistry as well as research that shows a significant advance in the organic chemistry or molecular design aspects of chemical biology, catalysis, supramolecular and macromolecular chemistry, theoretical chemistry, mechanism-oriented physical organic chemistry, medicinal chemistry or natural products. Articles published in the journal should report new work which makes a highly-significant impact in the field. Routine and incremental work is generally not suitable for publication in the journal. More details about key areas of our scope are below. In all cases authors should include in their article clear rationale for why their research has been carried out.










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