5-Chlorocoumaranone-Conjugates as Chemiluminescent Protecting Groups (CLPG) and Precursors to Fluorescent Protecting Groups (FPG)

Abstract

The introduction and cleavage of protecting groups and the subsequent release of protected molecules is an important tool in synthetic organic chemistry. When polyfunctionalized substrates are involved, the reactivity of similar functional groups must be differentiated and selectively switched on and off. A very useful switching agent is visible or UV-light in photoremovable protecting groups (PRPG), allowing the PG release upon interaction with electromagnetic radiation. The reverse principle is the release of a protected molecule, which is accompanied by emission of light, i.e., chemiluminescent protecting groups (CLPG). This principle is proposed and investigated for phenylalanine (using ureido carboxylic acid 2 and its methyl ester derivative 3) and the carbamate derivatives of paracetamol 4 and L-menthol 7, protected as the corresponding urea-/carbamate-coumaranones 5A, 5E, 6 and 8, respectively. While the carbamate derivative 6 released the protected substrate with a short and strong emission of blue light when treated with a base under atmospheric oxygen, 8 had to be treated additionally with potassium hydroxide in boiling ethanol to completely cleave the PG. Both urea-coumaranone derivatives 5A/5E had a flash-like CL without release of the protected amino acid and, thus, were converted into a fluorescent protecting group (FPG).