Synthesis of spirocyclic orthoesters by 'anomalous' rhodium(II)-catalysed intramolecular C-H insertions
Author(s)
Lombard, Fanny J
Lepage, Romain J
Schwartz, Brett D
Johnston, Ryne C
Healy, Peter C
Krenske, Elizabeth H
Coster, Mark J
Griffith University Author(s)
Year published
2018
Metadata
Show full item recordAbstract
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.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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Journal Title
Organic & Biomolecular Chemistry
Volume
16
Issue
2
Subject
Medicinal and biomolecular chemistry
Medicinal and biomolecular chemistry not elsewhere classified
Organic chemistry