Synthesis of spirocyclic orthoesters by 'anomalous' rhodium(ii)-catalysed intramolecular C-H insertionsElectronic supplementary information (ESI) available: General experimental procedures, computational methods and data, X-ray crystallographic data and X-ray structure of 11a. CCDC 1476765. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7ob02123b

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 th...

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Main Authors: Lombard, Fanny J, Lepage, Romain J, Schwartz, Brett D, Johnston, Ryne C, Healy, Peter C, Krenske, Elizabeth H, Coster, Mark J
Format: Article
Language:English
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Summary: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. Spirocyclic orthoesters are synthesised by 'anomalous' Rh( ii )-catalysed intramolecular C-H insertion reactions.
ISSN:1477-0520
1477-0539
DOI:10.1039/c7ob02123b