Intramolecular Ring-Expansion Reaction (RER) and Intermolecular Coordination of In Situ Generated Cyclic (Amino)(aryl)carbenes (cAArCs).

ABSTRACT: Cyclic (amino)(aryl)carbenes (cAArCs) based on the isoindoline core were successfully generated in situ by α-elimination of 3-alkoxyisoindolines at high temperatures or by deprotonation of isoindol-2-ium chlorides with sodium or copper(I) acetates at low temperatures. 3-Alkoxy-isoindolines 2 a,b-OR (R=Me, Et, iPr) have been prepared in high yields by the addition of a solution of 2-aryl-1,1-diphenylisoindol-2-ium triflate (1 a,b-OTf; a: aryl=Dipp=2,6-diisopropylphenyl; b: Mesityl-, Mes=2,4,6-trimethylphenyl) to the corresponding alcohol (ROH) with NEt₃ at room temperature. Furthermore, the reaction of 2 a,b-OMe in diethyl ether with a tenfold excess of hydrochloric acid led to the isolation of the isoindol-2-ium chlorides 1 a,b-Cl in high yields. The thermally generated cAArC re

SUBMITTER: Lorkowski J 

PROVIDER: S-EPMC6771577 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature