Recent advances in catalytic asymmetric [1,3]-rearrangement reactions

Abstract

This review covering the recent advances of asymmetric 1,3-rearrangement reactions is divided into four different fields, including transition metal catalysis, nucleophilic catalysis, Brønsted acid catalysis and Lewis acid catalysis.

Asymmetric catalytic [1,3]- or [3,3]-sigmatropic rearrangement of 3-allyloxy-4H-chromenones and their analogues

“…The regioselectivity of O-to-C-sigmatropic rearrangement shows bias to both acidity and steric hindrance of the Lewis acid catalysts, and the intrinsic property of the allyl vinyl ethers (Scheme 1a). Catalytic asymmetric versions of the [3,3]- and [1,3]-rearrangements have made achievements in recent years, 7,8 but the chiral catalytic system which is tolerant to both [1,3]- and [3,3]-rearrangements is elusive due to the diverse reaction pathways.…”

Radical-triggered base-free 1,3-C → C migrations: chemodivergent synthesis of cyclic imines from N-allyl enamines

“…1). 6,7 Among the few reported [1,3]-migrations, migrations between heteroatoms (N → N or O → N migrations, etc.) 8 or between hetero-and carbon atoms (O → C 7,9 or N → C 10 migrations, etc.)…”

“…6,7 Among the few reported [1,3]-migrations, migrations between heteroatoms (N → N or O → N migrations, etc.) 8 or between hetero-and carbon atoms (O → C 7,9 or N → C 10 migrations, etc.) have been the focus, for example, Fries rearrangements via 1,3-O → C migrations and related N → C and S → C migrations.…”