Sulfur atom effect on the photochemical release of benzylamine from caged amines

Abstract

Abstract Carbamate linkers are commonly used to attach photolabile protecting groups (PPGs) to amine functional groups. However, the release of amines from the carbamate linkage has low photochemical quantum yields because of the low leaving ability of the carbamic anion. In this study, we synthesized a new coumarin-based thiocarbamate-containing caged amine as a model to study the effect of sulfur on the photocleavage of the amine from the PPG. The release of the amine from the thiocarbamate (−SC(O)NHCH2Ph) linkage was ∼20 times faster than from the carbamate (−OC(O)NHCH2Ph) linkage.