6533b831fe1ef96bd1298495

RESEARCH PRODUCT

Reactivity and Selectivity of Ortho-Metalated Rhodium(II) Complexes in C−H Insertion Reactions of α-Diazo Compounds

Julia Pérez-prietoFrancisco EstevanSalah-eddine StiribaInés PereiraPascual Lahuerta

subject

ChemistryOrganic ChemistryRegioselectivitychemistry.chemical_elementMedicinal chemistryRhodiumInorganic Chemistrychemistry.chemical_compoundInsertion reactionIntramolecular forceDiazoReactivity (chemistry)Physical and Theoretical ChemistrySelectivityPhosphine

description

Regioselective intramolecular C−H insertion reactions of α-diazo β-keto esters and α-diazo ketones are mediated by Rh2[OOCR]4-x[PC]x (x = 1, 2; PC = ortho-metalated phosphine; R = CH3, C3F7). In particular, the intramolecular transformation of 1-diazo-5-methyl-3-propyl-2-hexanone catalyzed by Rh2[OOCCH3]2[PC]2 (PC = (C6H4)P(C6H5)2, head-to-tail (H−T) configuration) afforded only the tertiary C−H insertion product. By comparison, no C−H insertion reaction was promoted by doubly metalated complexes with a head-to-head (H−H) configuration. Rh2[OOCR]3[PC] compounds were found to be less suited for these type of reactions.

yearjournalcountryeditionlanguage
1998-07-07Organometallics
https://doi.org/10.1021/om971070q