Owing to its diverse activation processes including single-electron transfer (SET) and hydrogen-atom (HAT), visible-light photocatalysis has emerged as a sustainable efficient platform for organic synthesis. These provide powerful avenue the direct functionalization of C(sp3)–H bonds under mild conditions. Over past decade, there have been remarkable advances in enantioselective bond via combined with conventional asymmetric catalysis. Herein, we summarize involving discuss two main pathways...

A photocatalytic cascade cyclization of 1,7-enynes with acyl chlorides has been established. This method offers an operationally simple access to diverse fused pyran derivatives a broad substrate scope in high yields from via radical intermediate.

The intramolecular 1,5-H transfer reaction of aryl iodides has been realized through visible-light photoredox catalysis.

Abstract Herein we describe a mild method for the dual C(sp 3 )−H bond functionalization of saturated nitrogen‐containing heterocycles through sequential visible‐light photocatalyzed dehydrogenation/[2+2] cycloaddition procedure. As complementary approach to well‐established use iminium ion and α‐amino radical intermediates, elusive cyclic enamine intermediates were effectively generated by photoredox catalysis under conditions efficiently captured acetylene esters form wide array bicyclic...

A powerful cascade reaction was developed for the synthesis of chromeno[4,3-b]pyrrolidines with high yields and excellent stereoselectivities. This efficient expeditiously established two fused rings which bear three contiguous stereogenic centers including one quaternary stereocenter in a single operation low catalyst loading under mild conditions.

Herein, we report a general strategy for the rational design of an efficient organic photocatalyst, and describe robust method direct C(sp3)–H carbamoylation saturated aza-heterocycles under mild conditions by using naphthalimide (NI)-based photocatalyst. This protocol provides concise practical approach rapid installation valuable amide bond onto pharmaceutically useful to access wide range cyclic α-amino amides. A series mechanism investigations have demonstrated this transformation...

Described herein is the first example of application an iminium intermediate generated by visible-light photocatalyzed oxidation in inverse electron-demand aza-Diels-Alder reaction. This dual functionalization both C(sp(3))-H and C(sp(2))-H bonds N-aryl tetrahydroisoquinolines represents a valuable for access to polycycles with high diastereoselectivity.

The first highly enantioselective α-fluorination of 2-acyl imidazoles utilizing iridium catalysis has been accomplished. This transformation features mild conditions and a remarkably broad substrate scope, providing an efficient approach to obtain wide range fluorine-containing which are found in variety bioactive compounds prodrugs. A large scale synthesis also tested demonstrate the potential utility this fluorination method.

A novel visible-light-induced aza-pinacol rearrangement was developed for the first time. In this approach, addition of N-centered radical to C═C bond alkylidenecyclopropanes delivers a variety cyclobutanimines and γ-butyrolactones, with all-carbon quaternary centers via ring expansion cyclopropyl group, in moderate good yields under mild reaction conditions.

A series of inexpensive, easily tunable, and highly reducing organic photocatalysts (PCs) that exhibit strong absorption in the visible region are described. Time-dependent density functional theory calculations were applied to corroborate experimental observations explain relationship between structure property. The photocatalytic efficiency these PCs was demonstrated by catalyzing several challenging reactions radical cascade cyclization 1,6-diyne with superior other photocatalysts.

Herein, we describe a novel and efficient method for constructing series of fluorine-containing γ-keto acid derivatives through combining visible-light photoredox catalysis chiral Lewis catalysis. With this dual catalytic strategy, variety amides containing gem-difluoroalkyl group α,β-unsaturated-γ-keto esters were successfully constructed with high stereoselectivities, respectively. A experiments showed that the chemoselectivity process was highly dependent on fluorine reagents besides...

A method using aroyl chlorides as atom-transfer radical cyclization agents in a novel visible-light photocatalytic aroylchlorination reaction is developed. The overall transformation involves the formation of two new C–C bonds and one C–Cl bond one-pot process. advantages this include high atom/step/redox economy, mild conditions, operational simplicity, broad substrate scopes.

Here we describe an unprecedented metal-free C(sp3)–H aroylation of amines via visible-light photoredox catalysis, which provides a straightforward route for the construction useful α-amino aryl ketone skeleton. Additionally, number selected products exhibit good biological activity protecting PC12 cell damage, shows that this skeleton has potential to become new neuroprotective agent. Finally, series mechanism experiments indicate transformation undergoes catalytic radical–radical...

A protocol for the chemically divergent synthesis of β-lactams and α-amino acid derivatives with isothiourea (ITU) catalysis by switching solvents was developed. The stereospecific Mannich reaction occurring between imine C(1)-ammonium enolate generated zwitterionic intermediates, which underwent intramolecular lactamization afforded β-lactam when DCM CH3CN were used as solvents. However, EtOH solvent, intermediates an intermolecular esterification reaction, produced. Detailed mechanistic...

We have developed a metal-free, visible-light driven chiral phosphoric acid catalyzed asymmetric intermolecular, three-component radical-initiated dicarbofunctionalization and oxytrifluoromethylation of enamines.

Here we describe a metal-free amino-heteroarylation of unactivated olefins via organic photoredox catalysis, providing concise and efficient approach for the rapid synthesis various δ (β, ε)-amino ketones under mild conditions. This protocol demonstrates that new photocatalyst Cz-NI developed by our group has an excellent catalytic performance. Finally, series mechanistic experiments DFT calculations indicate this transformation undergoes sequential radical addition/functional migration process.

A visible-light-promoted metal-free alkylheteroarylation of unactivated olefins was developed by using readily available ketones/esters as the alkyl radical source. With this strategy, both linear and cyclic could be conveniently converted to corresponding α-carbonyl species commonly found diacylperoxide (LPO) hydrogen atom transfer reagent, heteroaryl-containing 1,7-carbonyl compounds were synthesized via distal heteroaryl ipso-migration in good excellent yields with high functional group...

An efficient method was successfully developed to obtain cyclic β-amino ketones via visible-light photoredox catalysis. With this catalytic system, vinyl azides and N-Ph pyrrolidines react form by α-amino radical addition. This provides a simple, mild, straightforward, novel paradigm prepare important ketones.

Herein, we report a photoinduced dehydrogenation/(3+2) cycloaddition reaction by merging organic photoredox and Lewis acid catalysis, providing straightforward efficient approach for directly installing benzofuran skeleton on the saturated aza-heterocycles. In this protocol, also describe novel photocatalyst (t-Bu-DCQ) with advantages of wider redox potential, easy synthesis, low price. Furthermore, stepwise activation mechanism dual C(sp3)-H bonds was demonstrated series experimental...

Organophotoredox catalytic four-component radical-polar crossover cascade reactions for the stereoselective synthesis of β-amido sulfones with high atom-, step-, and redox economy excellent diastereoselectivity.

A PPh3 mediated reductive annulation reaction between isatins and 4,4-dicyano-2-methylenebut-3-enoates was developed. The provided an alternative method for constructing five- three-membered all-carbon spirooxindole compounds. Lithium chloride as a Lewis acid played key role in the synthesis of spirocyclopentenyl oxindole

We herein report a general organocatalytic enantioselective strategy for the construction of highly strained spiro[2,3]hexane skeletons from methylenecyclopropanes and broad selection α,β-unsaturated aldehydes. The reaction proceeds through Michael addition followed by ring expansion nucleophilic attack an enamine to realize spiro[2,3]hexanes. Key success this approach are utilization electron-deficient difluoro-substituted secondary amine catalyst intrinsic reactivity methylenecyclopropanes.

A mild metal-free C-N bond activation strategy for the direct conversion of inert tertiary amines with acyl chlorides into amides via organic photoredox catalysis is presented. In this protocol, a novel photocatalyst (Cz-NI-Ph) that showed excellent catalytic performance during cleavage developed. Moreover, reaction features green and conditions, broad substrate scope, readily available raw materials.

Herein, we describe the photocatalytic generation of nucleophilic aroyl radicals from simple chlorides as a universal and efficient cross-coupling strategy for direct aroylation heteroarenes. Furthermore, visible light-mediated alkylation heteroarenes has also been achieved using unactivated bromoalkanes radical precursors. These two strategies feature high functional group tolerance, exclusive regioselectivity reaction at more electrophilic position heteroarenes, easily accessible...