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Intramolecular hydride transfer onto arynes: redox-neutral and transition metal-free C(sp3)-H functionalization of amines.

ABSTRACT: Transition metal-free intramolecular hydride transfer onto arynes is reported for the first time. This unique transformation is utilized in redox-neutral intermolecular ?-functionalization reactions of different tertiary amines, generating C(sp3)-C(sp3/sp2/sp) bonds in a single synthetic operation. Deuterium labeling studies support initial cleavage of the ?-C-H bond via intramolecular 1,5-hydride transfer onto the aryne, which leads to activation of a range of integrated pronucleophiles and ultimately affords a new approach to cross-dehydrogenative coupling reactions which utilize aryne intermediates.

SUBMITTER: Idiris FIM 

PROVIDER: S-EPMC5914459 | biostudies-literature | 2018 Mar

REPOSITORIES: biostudies-literature

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Intramolecular hydride transfer onto arynes: redox-neutral and transition metal-free C(sp<sup>3</sup>)-H functionalization of amines.

Idiris Fahima I M FIM   Majesté Cécile E CE   Craven Gregory B GB   Jones Christopher R CR  

Chemical science 20180208 11

Transition metal-free intramolecular hydride transfer onto arynes is reported for the first time. This unique transformation is utilized in redox-neutral intermolecular α-functionalization reactions of different tertiary amines, generating C(sp<sup>3</sup>)-C(sp<sup>3</sup>/sp<sup>2</sup>/sp) bonds in a single synthetic operation. Deuterium labeling studies support initial cleavage of the α-C-H bond <i>via</i> intramolecular 1,5-hydride transfer onto the aryne, which leads to activation of a ran  ...[more]

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