Stereoselective two-carbon ring expansion of allylic amines via electronic control of palladium-promoted equilibria

Abstract

General methodologies enabling the two-carbon homologation of pyrrolidine and piperidine systems have yet to be developed. Herein we report that palladium-catalysed allylic amine rearrangements enable efficient two-carbon ring expansion of...

Ruthenium-Catalyzed Carbonylation of α-Aminoaryl-Tethered Alkylidenecyclopropanes: Synthesis of Eight-Membered Benzolactams

“…However, the synthesis of such units is of great challenge because of the unfavorable transannular interactions and entropic barriers in the transition state . The most widely used strategies for constructing this type of skeleton were based on ring-closing metathesis and ring expansion reactions . However, some other methods, such as intramolecular Claisen rearrangement, carbonylation reaction and others, have also been exploited.…”

Iridium-Catalyzed 1,3-Rearrangement of Allylic Ethers

“…Additionally, the 1,3-rearrangement of allylic alcohols has been well developed and has been accomplished in the presence of metal–oxygen, Ru, Ir, or Brønsted acids (Scheme a) . However, research concerning the 1,3-rearrangement of allylic alcohol derivatives is relatively rare, and the reported methods are only suitable for ring-contraction reactions. , Compared with that of allylic alcohols, the 1,3-rearrangement of allylic ethers is very challenging. In order to realize such a transformation, the following key questions should be addressed: (1) Realizing the cleavage of the inert C–O bond in allylic ether and the subsequent rearrangement with the same catalyst is challenging.…”