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The α-tertiary amine motif drives remarkable selectivity for Pd-catalyzed carbonylation of β-methylene C-H bonds.

ABSTRACT: The selective C-H carbonylation of methylene bonds in the presence of traditionally more reactive methyl C-H and C(sp²)-H bonds in α-tertiary amines is reported. The exceptional selectivity is driven by the bulky α-tertiary amine motif, which we hypothesise orientates the activating C-H bond proximal to Pd in order to avoid an unfavourable steric clash with a second α-tertiary amine on the Pd centre, promoting preferential cyclopalladation at the methylene position. The reaction tolerates a range of structurally interesting and synthetically versatile functional groups, delivering the corresponding β-lactam products in good to excellent yields.

SUBMITTER: Hogg KF

PROVIDER: S-EPMC5855970 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature

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The α-tertiary amine motif drives remarkable selectivity for Pd-catalyzed carbonylation of β-methylene C-H bonds.

Hogg Kirsten F KF Trowbridge Aaron A Trowbridge Aaron A Alvarez-Pérez Andrea A Gaunt Matthew J MJ

Chemical science 20171009 12

The selective C-H carbonylation of methylene bonds in the presence of traditionally more reactive methyl C-H and C(sp2)-H bonds in α-tertiary amines is reported. The exceptional selectivity is driven by the bulky α-tertiary amine motif, which we hypothesise orientates the activating C-H bond proximal to Pd in order to avoid an unfavourable steric clash with a second α-tertiary amine on the Pd centre, promoting preferential cyclopalladation at the methylene position. The reaction toler ...[more]

PMID: 29568467

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