Herein, we developed an efficient and green method for the synthesis of various alkyl amines via C(sp3)−S bond cleavage of vinylsulfonium salts. The reaction proceeds under an air atmosphere with...
A procedure for the synthesis of 1,2-diamines from vinyl
sulfonium
salts and arylamines under mild conditions was developed. This present
synthetic protocol not only obviates the need for a transition-metal
catalyst and an oxidizing reagent but also features a broad substrates
scope. The practicability of this protocol is demonstrated by the
one-pot synthesis, a scale-up reaction, and transformations of the
products to diverse N-heterocyclic compounds. Mechanistic
studies indicate that the formation of aziridine plays a key role
during this diamination process.
Activation of the IRE-1/XBP-1 pathway is related to many human diseases. Coumarin-based derivatives acting as both IRE-1 inhibitors and bright fluorophores are highly desirable to establish an integrated fluorescent inhibitor system. Here, we take insights into the aqueous stability of a photocaged IRE-1 inhibitor PC-D-F07 through a structure activity relationship. The substituent effects indicate that the electron-withdrawing −NO 2 moiety in the photocage combined with the tricyclic coumarin fluorophore contribute to the structural stability of PC-D-F07. To optimize the photocage of PC-D-F07, we incorporate a 1-ethyl-2nitrobenzyl or 2-nitrobenzyl photolabile moiety on the hydroxyl group of the IRE-1 inhibitor to generate RF-7 and RF-8. Upon photoactivation, both RF-7 and RF-8 present an increased fluorescence response, sequentially enabling the unlocking of the ortho-1,3-dioxane acetal for the release of active IRE-1 inhibitors. Moreover, RF-7 exhibits a high repolarization ratio of converting M2-type tumor-associated macrophages (M2-TAMs) to M1-type immuneresponsive macrophages. This provides a novel prodrug strategy of modulating druggable fluorophore backbones to achieve spatiotemporally controllable drug release for precise cancer treatment.
Metal-free allylic C(sp3)−H alkylation of branched α-styryl sulfonium salts based on [2,3]-sigmatropic rearrangement strategies has been developed. This operationally simple protocol enables allylic C(sp3)−H alkylation of a wide range of...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.