Asymmetric 1,n-Remote Aminoacetoxylation of Unactivated Internal Alkenes Enabled by Palladium Catalysis*

Guosheng Liu; Xintuo Yang; Pinhong Chen

doi:10.1002/anie.202408305

Asymmetric 1,n-Remote Aminoacetoxylation of Unactivated Internal Alkenes Enabled by Palladium Catalysis*

Angew Chem Int Ed Engl. 2024 May 17:e202408305. doi: 10.1002/anie.202408305. Online ahead of print.

Authors

Guosheng Liu¹, Xintuo Yang², Pinhong Chen³

Affiliations

¹ Shanghai Institute of Organic Chemsitry, Chinese Academy of Science, State Key Laboratory of Organometallics Chemistry, 345 Lingling Road, 200032, Shanghai, CHINA.
² Chinese Academy of Sciences Shanghai Institute of Organic Chemistry, State Key Laboratory of Organometallic Chemistry, Shanghai, CHINA.
³ Chinese Academy of Sciences Shanghai Institute of Organic Chemistry, State Key Laboratory of Organometallic Chemistry, 345 Lingling Road, 200032, CHINA.

PMID: 38760326
DOI: 10.1002/anie.202408305

Abstract

A palladium -catalyzed asymmetric 1,n-remote aminoacetoxylation of cis-alkenes has been developed using PhI(OAc)2 as oxidant, providing the acetoxylated lactams with excellent enantioselectivities under mild reaction conditions. The sterically hindered pyridine-oxazoline (Pyox) L3 with a tert-butyl group in oxazoline ring and propyl group in C6 position of pyridinyl is vital for the reaction, where the former is good for asymmetric aminopalladation step and the latter for the chain walking process. The enantioenriched lactam products were proven to be good building blocks for the synthesis of azabicycles.

Keywords: Azabicycles; Cis-alkenes; Enantioenriched lactam; Enantioselective remote aminoacetoxylation; Palladium Catalysis.