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Allyl sulfones are an essential pharmacophore in many bioactive compounds. To combat their synthetic barrier, we report a practical, straightforward organophotocatalyzed methodology for accessing miscellaneously functionalized allyl sulfone derivatives using inexpensive and bench‐stable sodium sulfinate salts under mild conditions. This photo‐catalyzed radical sulfonylation provides access to a variety of allyl sulfones in good to excellent yields with high E : Z selectivity. A wide range of vinyl cyclopropanes, as well as aryl/hetero and alkyl sodium sulfinates, were tolerated and reliable in gram‐scale synthesis. Later on, further functionalization of allyl sulfones was demonstrated. A plausible mechanism for radical sulfonylation is proposed from the control experiments. [ABSTRACT FROM AUTHOR]

Herein, we present a remarkably efficient, highly diastereoselective organophotoredox-catalyzed hydrosulfonylation of cyclopropenes. This method employs sodium sulfinates to successfully construct poly-substituted sulfonated cyclopropane derivatives. To enhance the applicability of this transformation, we demonstrate its broad applicability across a wide range of substrates, its scalability for large-scale synthesis, and its compatibility with late-stage functionalization. Notably, this late-stage functionalization protocol exhibits good tolerance toward diverse functional groups. Its operational convenience further adds to its appeal, providing access to valuable building blocks that hold great significance in drug discovery and medicinal chemistry. [ABSTRACT FROM AUTHOR]

A metal-free approach for C(sp3)–H activation followed by an intramolecular Giese reaction to construct a wide range of cyclic ether scaffolds of various ring sizes under environmentally benign and straightforward conditions is reported. An easily prepared pyrylium salt is employed as an organophotocatalyst for this visible-light-driven, highly atom-economical (PMI = 64.34 g/g for a 0.2 mmol scale), cost-effective, and chemoselective transformation. The reported method has a broad functional-group tolerance, resulting in good-quality products. Furthermore, downstream functionalizations of a product and a gram-scale synthesis (PMI = 17.41 g/g for a 10 mmol scale) are demonstrated, highlighting our method's advantages. [ABSTRACT FROM AUTHOR]

Tandem, one‐pot, multicomponent reaction for direct α‐C(sp3)−H alkylation of phosphoramides and thiophosphoramides scaffolds are illustrated. The basic nature of phosphoramide leads to a diverse set of in situ generated Michael acceptors making the reactions highly atom and step economical. The reaction conditions are mild, entirely metal‐ and external additives free. Alkylated phosphoramides were obtained with good yields and selectivity using visible‐light organo‐photocatalysis. [ABSTRACT FROM AUTHOR]

Integrating of the trifluoroethyl (-CH 2 CF 3 ) group into the organic compounds by activating the distal C( sp 3 )-H bond is a challenging but crucial task in organic chemistry. This transformation imparts unique physicochemical properties to the compounds, such as enhanced lipophilicity, metabolic stability, and altered electronic characteristics. In this study, we unveil a new palladium-catalyzed method to directly introduce the trifluoroethyl group into amino acid and carboxylic acid derivatives. Remarkably, this method effectively activates the β- C( sp 3 )-H bond across various substrates at room temperature. Utilizing mesityl(2,2,2-trifluoroethyl)iodonium triflate as a trifluoroethyl source, our approach selectively targets the distal β- C( sp 3 )-H bonds of amino and carboxylic acids, ensuring high chemoselectivity and enabling the straightforward synthesis of a diverse array of important γ-trifluoromethyl amino acid and carboxylic acid derivatives. Furthermore, the practical applicability of this methodology is demonstrated through its scalability for gram-scale synthesis.

A visible-light-driven organophotocatalyzed multicomponent approach has been developed for tandem direct C(sp 3 )-H activation and alkylation followed by trifluoromethylthiolation in a one-pot operation. We report a completely metal-free, tandem, three-component approach for the difunctionalization of activated alkenes via the photoinduced radical pathway. This protocol allows the formation of two new C(sp 3 )-C(sp 3 ) and C(sp 3 )-SCF 3 bonds using a bench-stable, easy-to-handle trifluoromethylthiolating reagent under mild reaction conditions. The generosity of this reaction is shown with a library of C(sp 3 )-H donors and alkenes derivatives. The reaction conditions can tolerate a wide variety of functional groups. Gram-scale synthesis using environmentally benign and straightforward conditions highlights the synthetic advancement of the methodology. Further functionalization of the final product is also successfully demonstrated.

A photocatalytic metal-free, visible-light-driven, highly atom-economic, direct multiple α-C(sp 3 )-H alkylation of phosphoramides and thiophosphoramides is demonstrated under environmentally benign conditions. Economically viable and commercially available Eosin-Y is used as an HAT photocatalyst for mono-α-C(sp 3 )-H alkylation of phosphoramide derivatives. Remarkably, di- and tri-C(sp 3 )-H alkylation of phosphoramides and thiophosphoramides using an acridinium photocatalyst is reported with good yield and selectivity. Mechanistic studies reveal that monoalkylation of phosphoramides by Eosin-Y follows the HAT mechanism, whereas di- and tri-C(sp 3 )-H alkylation by the acridinium photocatalyst follows the SET mechanism.