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

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...

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Published inOrganic & biomolecular chemistry Vol. 16; no. 2; pp. 256 - 261
Main Authors Lombard, Fanny J., Lepage, Romain J., Schwartz, Brett D., Johnston, Ryne C., Healy, Peter C., Krenske, Elizabeth H., Coster, Mark J.
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 2018
Royal Society of Chemistry
Subjects
Bonding
Chemical synthesis
Chemistry
Chemistry, Organic
Density functional theory
Forming
Orthoesters
Physical Sciences
Rhodium
Science & Technology
Zwitterions
OXIDATION
OXYGEN
DESIGN
MECHANISM
PRODUCTS
DIAZO COMPOUND
REACTIVITY
CHEMISTRY
SPIROACETALS
RHODIUM CARBENOIDS
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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.
Bibliography:Australian Research Council
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ISSN:1477-0520
1477-0539
DOI:10.1039/c7ob02123b