Revisiting Arene C(sp2 )-H Amidation by Intramolecular Transfer of Iridium Nitrenoids: Evidence for a Spirocyclization Pathway

Yeongyu Hwang; Yoonsu Park; Yeong Bum Kim; Dongwook Kim; Sukbok Chang

doi:10.1002/anie.201808892

Revisiting Arene C(sp² )-H Amidation by Intramolecular Transfer of Iridium Nitrenoids: Evidence for a Spirocyclization Pathway

Angew Chem Int Ed Engl. 2018 Oct 8;57(41):13565-13569. doi: 10.1002/anie.201808892. Epub 2018 Sep 17.

Authors

Yeongyu Hwang^{1

2}, Yoonsu Park^{1

2}, Yeong Bum Kim^{1

2}, Dongwook Kim^{1

2}, Sukbok Chang^{1

2}

Affiliations

¹ Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141, Republic of Korea.
² Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon, 34141, Republic of Korea.

PMID: 30151953
DOI: 10.1002/anie.201808892

Abstract

Two mechanistic pathways, that is, electrocyclization and electrophilic aromatic substitution, are operative in most intramolecular C-H amination reactions proceeding by metal nitrenoid catalysis. Reported here is an alternative mechanistic scaffold leading to benzofused δ-lactams selectively. Integrated experimental and computational analysis revealed that the reaction proceeds by a key spirocyclization step followed by a skeletal rearrangement. Based on this mechanistic insight, a new synthetic route to spirolactams has been developed.

Keywords: C−H amidation; iridium; reaction mechanisms; rearrangements; spirocompounds.

Publication types

Research Support, Non-U.S. Gov't