title: Palladium-Catalyzed Ring Expansion of Spirocyclopropanes to Form Caprolactams and Azepanes.
abstract: A palladium(0)-catalyzed rearrangement of piperidones and piperidines bearing a spirocyclopropane ring was developed. The ring expansion reaction led to a variety of functionalized caprolactam and azepane products in good to excellent yields. Experimental and computational mechanistic studies revealed an initial oxidative addition of the distal carbon-carbon bond of a cyclopropane ring to the palladium(0) catalyst and the relief of ring strain as a driving force for product formation.
authors.affiliation: Genentech, Incorporated , Discovery Chemistry, 1 DNA Way, South San Francisco, California 94080, United States.
authors.forename: Olivier
authors.initials: O
authors.lastname: René
authors.affiliation: Genentech, Incorporated , Discovery Chemistry, 1 DNA Way, South San Francisco, California 94080, United States.
authors.forename: Iain A
authors.initials: IA
authors.lastname: Stepek
authors.affiliation: Genentech, Incorporated , Discovery Chemistry, 1 DNA Way, South San Francisco, California 94080, United States.
authors.forename: Alberto
authors.initials: A
authors.lastname: Gobbi
authors.affiliation: Genentech, Incorporated , Discovery Chemistry, 1 DNA Way, South San Francisco, California 94080, United States.
authors.forename: Benjamin P
authors.initials: BP
authors.lastname: Fauber
authors.affiliation: Argenta , Discovery Services, Charles River, 7-9 Spire Green Centre, Flex Meadow, Harlow, Essex CM19 5TR, United Kingdom.
authors.forename: Simon
authors.initials: S
authors.lastname: Gaines