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.

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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...