Elaborating Complex Heteroaryl‐Containing Cycles via Enantioselective Palladium‐Catalyzed Cycloadditions

Abstract

Ag eneral method for asymmetric synthesis of heteroaryl-containing cycles via palladium-catalyzed cyclization is reported. Most classes of nitrogen-containing aromatics, including pyridines,q uinolines,p yrimidines,v arious azoles and the derivatives of nucleobases are compatible substrates, offering various heteroaryl-substituted cyclopentane,p yrrolidine,f uranidine and bicyclo[4.3.1]decadiene derivatives with good to excellent enantioselectivity and diastereoselectivity.

Stereoselective synthesis and applications of spirocyclic oxindoles

“…Trost has also applied his development of Pd-allyl complexes previously discussed in the spiropyrrolidine section to the synthesis of spiroTHFs. 300 Similar to Moody's use of diazo compounds to synthesise spiropyrrolidines, OH insertion/cyclisation could be used to synthesise spiroTHFs 301 and there have been many other approaches using Rh-or Cu-catalysed decomposition of diazo compounds. 302 Ring expansion of small-rings.…”

Dearomatization of Nitro(hetero)arenes through Annulation

“…Subsequently, the same group further developed palladium‐catalyzed asymmetric annulation reactions of trimethylenemethane bearing nitrogen‐containing aromatics (e. g., pyridines, quinolines, pyrimidines, various azoles and the derivatives of nucleobases) and electron‐deficient double bonds (e. g., α,β‐unsaturated carbonyl compounds, nitroolefins and imines), securing a wide range of chiral heteroaryl‐substituted cycles in high yields and with excellent diastereo‐ and enantioselectivities. Dearomative [3+2] annulation was also successful with 8‐nitroquinoline as the acceptor, and the desired fused ring was obtained with excellent yield, enantioselectivity and diastereoselectivity (Scheme 32B) [46b] …”