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Isodesmic reactions, in which chemical bonds are redistributed between substrates and products, provide a general and powerful strategy for both biological and chemical synthesis. However, most isodesmic reactions involve either metathesis or functional-group transfer. Here, we serendipitously discovered a novel isodesmic reaction of indoles and anilines that proceeds intramolecularly under weakly acidic conditions. In this process, the five-membered ring of the indole motif is broken and a new indole motif is constructed on the aniline side, accompanied by the formation of a new aniline motif. Mechanistic studies revealed the pivotal role of σ→π* hyperconjugation on the nitrogen atom of the indole motif in driving this unusual isodesmic reaction. Furthermore, we successfully synthesized a diverse series of polycyclic indole derivatives; among quinolines, potential antitumor agents were identified using cellular and in vivo experiments, thereby demonstrating the synthetic utility of the developed methodology., (© 2024 Wiley‐VCH GmbH.)

Radical-involved multicomponent difunctionalization of 1,3-dienes has recently emerged as a promising strategy for rapid synthesis of valuable allylic compounds in one-pot operation. However, the expansion of radical scope and enantiocontrol remain two major challenges. Herein, we describe an unprecedented photoinduced copper-catalyzed highly enantioselective three-component radical 1,2-azidooxygenation of 1,3-dienes with readily available azidobenziodazolone reagent and carboxylic acids. This mild protocol exhibits a broad substrate scope, high functional group tolerance, and exceptional control over chemo-, regio- and enantioselectivity, providing practical access to diverse valuable azidated chiral allylic esters. Mechanistic studies imply that the chiral copper complex is implicated as a bifunctional catalyst in both the photoredox catalyzed azidyl radical generation and enantioselective radical C-O cross-coupling., (© 2024 Wiley-VCH GmbH.)

Radical-involved arylative cross-coupling reactions have recently emerged as an attractive strategy to access valuable aryl-substituted motifs. However, there still exist several challenges such as limited scope of radical precursors/acceptors, and lack of general asymmetric catalytic systems, especially regarding the multicomponent variants. Herein, we reported a general copper-Box system for asymmetric three-component arylative radical cross-coupling of vinylarenes and 1,3-enynes, with oxime carbonates and aryl boronic acids. The reactions proceed under practical conditions in the absence or presence of visible-light irradiation, affording chiral 1,1-diarylalkanes, benzylic alkynes and allenes with good enantioselectivities. Mechanistic studies imply that the copper/Box complexes play a dual role in both radical generation and ensuing asymmetric cross-coupling. In the cases of 1,3-enynes, visible-light irradiation could improve the activity of copper/Box complex toward the initial radical generation, enabling better efficiency match between radical formation and cross-coupling., (© 2024 Wiley‐VCH GmbH.)

Organic molecules bearing chiral sulfur stereocenters exert a great impact on asymmetric catalysis and synthesis, chiral drugs, and chiral materials. Compared with acyclic ones, the catalytic asymmetric synthesis of thio-heterocycles has largely lagged behind due to the lack of efficient synthetic strategies. Here we establish the first modular platform to access chiral thio-oxazolidinones via Pd-catalyzed asymmetric [3+2] annulations of vinylethylene carbonates with sulfinylanilines. This protocol is featured by readily available starting materials, and high enantio- and diastereoselectivity. In particular, an unusual effect of a non-chiral supporting ligand on the diastereoselectivity was observed. Possible reaction mechanisms and stereocontrol models were proposed., (© 2024 Wiley-VCH GmbH.)

The construction of an all-in-one catalyst, in which the photosensitizer and the transition metal site are close to each other, is important for improving the efficiency of metallaphotoredox catalysis. However, the development of convenient synthetic strategies for the precise construction of an all-in-one catalyst remains a challenging task due to the requirement of precise installation of the catalytic sites. Herein, we have successfully established a facile bottom-up strategy for the direct synthesis of Ni(II)-incorporated covalent organic framework (COF), named LZU-713@Ni, as a versatile all-in-one metallaphotoredox catalyst. LZU-713@Ni showed excellent activity and recyclability in the photoredox/nickel-catalyzed C-O, C-S, and C-P cross-coupling reactions. Notably, this catalyst displayed a better catalytic activity than its homogeneous analogues, physically mixed dual catalyst system, and, especially, LZU-713/Ni which was prepared through post-synthetic modification. The improved catalytic efficiency of LZU-713@Ni should be attributed to the implementation of bottom-up strategy, which incorporated the fixed, ordered, and abundant catalytic sites into its framework. This work sheds new light on the exploration of concise and effective strategies for the construction of multifunctional COF-based photocatalysts., (© 2023 Wiley-VCH GmbH.)

Vinyldiazo compounds are one of the most important synthons in the construction of a cyclic ring. Most photochemical transformations of vinyldiazo compounds are mainly focusing on utilization of their C═C bond site, while reactions taking place at terminal nitrogen atom are largely unexplored. Herein, a photocatalytic cascade radical cyclization of LBRs with vinyldiazo reagents through sequential B─N/C─N bond formation is described. The reaction starts with the addition of LBRs (Lewis base-boryl radicals) at diazo site, followed by intramolecular radical cyclization to access a wide range of important boron-handled pyrazoles in good to excellent yields. Control experiments, together with detailed mechanism studies well explain the observed reactivity. Further studies demonstrate the utility of this approach for applications in pharmaceutical and agrochemical research., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The exploration of value-added conversions of naturally abundant amino acids has received considerable attention from the synthetic community. Compared with the well-established asymmetric decarboxylative transformation, the asymmetric deaminative transformation of amino acids still remains a formidable challenge, mainly due to the lack of effective strategies for the C-N bond activation and the potential incompatibility with chiral catalysts. Here, we disclose a photoinduced Cu-catalyzed asymmetric deaminative coupling reaction of amino acids with arylboronic acids. This new protocol provides a series of significant chiral phenylacetamides in generally good yields and excellent stereoselectivity under mild and green conditions (42-85 % yields, up to 97 % ee). Experimental investigations and theoretical calculations were performed to reveal the crucial role of additional phenols in improving catalytic efficiency and enantiocontrol., (© 2023 Wiley-VCH GmbH.)

Radical single carbonylation reactions with CO constitute a direct and robust strategy toward various carbonyl compounds from readily available chemicals, and have been extensively studied over the past decades. However, realizing highly selective catalytic systems for controlled radical double carbonylation reactions has remained a substantial challenge, particularly for the more advanced multicomponent variants, despite their great potential value. Herein, we report a visible-light-driven radical relay five-component radical double aminocarbonylation reaction of unactivated alkenes using CO under metal-free conditions. This protocol provides direct access to valuable γ-trifluoromethyl α-ketoamides with good yields and high chemoselectivity. Crucial was the identification of distinct dual roles of amine coupling partners, sequentially acting as electron donors for the formation of photoactive electron donor-acceptor (EDA) complexes with radical precursors and then as a CO acceptor via nitrogen radical cations to form carbamoyl radicals. Cross-coupling of carbamoyl radicals with the acyl radicals that are formed in an alkene-based relay process affords double aminocarbonylation products., (© 2023 Wiley-VCH GmbH.)

Metal-polarized aza-ortho-quinone methides (aza-o-QMs) are a unique and efficient handle for azaheterocycle synthesis. Despite great achievements, the potential of these reactive intermediates has not yet been fully exploited, especially the new reaction modes. Herein, we disclosed an unprecedented dearomatization process of metal-polarized aza-o-QMs, affording transient dearomatized spiroaziridine intermediates. Based on this serendipity, we accomplished three sequential dearomatization-rearomatization reactions of benzimidazolines with aza-sulfur ylides, enabling the divergent synthesis of bis-nitrogen heterocycles with high efficiency and flexibility. Moreover, experimental and theoretical studies were performed to explain the proposed mechanisms and observed selectivity. Further cellular evaluation of the dibenzodiazepine products identified a hit compound for new antitumor drugs., (© 2023 Wiley-VCH GmbH.)

Catalytic and switchable C-H functionalization of N-heteroarenes under easily tunable conditions is a robust but challenging tool for the construction of biologically relevant compounds. Recently, a general electrochemical strategy has been developed for the direct C-H carboxylation of N-heteroarenes with CO 2 , and by simply choosing different types of cell setups, carboxylated products are furnished with excellent and tunable site selectivity. This study also paves the way for regulating the reactivity modes in electrochemical synthesis., (© 2023 Wiley-VCH GmbH.)

Ring-opening transformations of donor-acceptor (D-A) cyclopropanes enable the rapid assembly of complex molecules. However, the enantioselective formation of chiral quaternary stereocenters using substrates bearing two different acceptors remains a challenge. Herein, we describe the first palladium-catalyzed highly diastereo- and enantioselective (3+2) cycloaddition of vinyl cyclopropanes bearing two different electron-withdrawing groups, a subset of D-A cyclopropanes. The key to the success of this reaction is the remote stereoinduction through hydrogen bond from chiral ligands, which thereby addressed the aforementioned challenge. A variety of chiral five-membered heterocycles were produced in good yields and with high stereoselectivity (up to 99 % yields, 99 : 1 er and >19 : 1 dr). In-depth mechanistic investigations, including control experiments and theoretical calculations, revealed the origin of the stereoselectivity and the importance of H-bonding in stereocontrol., (© 2022 Wiley-VCH GmbH.)

Catalytic asymmetric synthesis of chiral endocyclic allenes remains a challenge in allene chemistry owing to unfavored tension and complex chirality. Here, we present a new relay strategy merging Pd-catalyzed asymmetric [3+2] annulation with enyne-Cope rearrangement, providing a facile route to chiral 9-membered endocyclic allenes with high efficiency and enantioselectivity. Moreover, theoretical calculations and experimental studies were performed to illustrate the critical, but unusual Cope rearrangement that allows for the complete central-to-axial chirality transfer., (© 2022 Wiley-VCH GmbH.)

A visible-light-driven and room temperature photo-Wolff-Kischner reaction of sulfur ylides and N-tosylhydrazones has been developed for the first time to provide modular access to alkene synthesis. The high functional group tolerance and broad substrate scope were demonstrated by more than 60 examples. Both E- and Z-olefinic stereochemistry in the products could be controlled with excellent stereoselectivity. A series of mechanistic studies support that the reaction should proceed through a radical-carbanion crossover pathway, specifically involving addition of photo-generated sulfur ylide radical cations to N-tosylhydrazones to form carbanions and subsequent Wolff-Kischner process., (© 2021 Wiley-VCH GmbH.)

Kharasch-Sosnovsky reaction is one of the most powerful methods for allylic oxidation of alkenes. However, the inherent radical mechanism and use of peroxides as both oxidants and oxygen nucleophiles render dearth of universal catalytic systems for highly enantioselective variants and limited scope. Herein, an alternative to the asymmetric Kharasch-Sosnovsky reaction that utilized a chiral copper catalyst and purple-LED irradiation to enable the three-component coupling of 1,3-dienes, oxime esters, and carboxylic acids is reported. This protocol features mild conditions, remarkable scope and functional group tolerance as evidenced by >80 examples and utility in the late-stage modification of pharmaceuticals and natural products. Detailed mechanistic studies provide evidences for the radical-based reaction pathway., (© 2021 Wiley-VCH GmbH.)

Vinylcyclopropanes (VCPs) are commonly used in transition-metal-catalyzed cycloadditions, and the utilization of their recently realized reactivities to construct new cyclic architectures is of great significance in modern synthetic chemistry. Herein, a palladium-catalyzed, visible-light-driven, asymmetric [5+2] cycloaddition of VCPs with α-diazoketones is accomplished by switching the reactivity of the Pd-containing dipolar intermediate from an all-carbon 1,3-dipole to an oxo-1,5-dipole. Enantioenriched seven-membered lactones were produced with good reaction efficiencies and selectivities (23 examples, 52-92 % yields with up to 99:1 er and 12.5:1 dr). In addition, computational investigations were performed to rationalize the observed high chemo- and periselectivities., (© 2020 Wiley-VCH GmbH.)

Higher-order cycloadditions, particularly [8+2] cycloadditions, are a straightforward and efficient strategy for constructing significant medium-sized architectures. Typically, configuration-restrained conjugated systems are utilized as 8π-components for higher-order concerted cycloadditions. However, for this reason, 10-membered monocyclic skeletons have never been constructed via catalytic asymmetric [8+2] cycloaddition with high peri- and stereoselectivity. Here, we accomplished an enantioselective [8+2] dipolar cycloaddition via the merger of visible-light activation and asymmetric palladium catalysis. This protocol provides a new route to 10-membered monocyclic architectures bearing chiral quaternary stereocenters with high chemo-, peri-, and enantioselectivity. The success of this strategy relied on the facile in situ generation of Pd-containing 1,8-dipoles and their enantioselective trapping by ketene dipolarophiles, which were formed in situ via a photo-Wolff rearrangement., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Chiral catalysts tolerating photochemical reactions are in great demand for the vast development of visible-light-induced asymmetric synthesis. Now, chiral octahedral complexes based on earth-abundant metal and chiral N 4 ligands are reported. One well-defined chiral Co II -complex is shown to be an efficient catalyst in the visible-light-induced conjugated addition of enones by alkyl and acyl radicals, providing synthetically valued chiral ketones and 1,4-dicarbonyls in 47->99 % yields with up to 97:3 e.r., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Catalytic asymmetric cycloadditions of ambident Pd-containing dipolar species with nucleophilic dipolarophiles, namely, inverse-electron-demand cycloadditions, are challenging and underdeveloped. Possibly, the inherent linear selectivity of Pd-catalyzed intermolecular allylations and the lack of efficient chiral ligands are responsible for this limitation. Herein, two cycloadditions of such intermediates with deconjugated butenolides and azlactones were accomplished by using a novel chiral hybrid P,S-ligand and hydrogen bonding. By doing so, highly functionalized, optically active dihydroquinol-2-ones were produced with generally high reaction efficiencies and selectivities. Preliminary DFT calculations were performed to explain the high enantio- and diastereoselectivities., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Alkene bifunctionalizations are powerful tools for the rapid construction of structurally complex and valuable scaffolds, and such reactions typically involve the use of transition-metal catalysts or organocatalysts. Here, we report for the first time a photogenerated neutral nitrogen radical catalyzed intermolecular alkene bifunctionalization by using allyl sulfones as the source of both the carbon and the sulfone functionalities under mild conditions. The key to the success of this protocol involves the visible-light-mediated photocatalytic in situ generation of a nitrogen-centered radical from the N-(2-acetylphenyl) benzenesulfonamide catalyst, and its activation of the allyl sulfones to generate reactive species. The preliminary control experiments supported the postulated mechanism., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The palladium-catalyzed Heck reaction is a well-known, Nobel Prize winning transformation for producing alkenes. Unlike the alkenyl and aryl variants of the Heck reaction, the alkyl-Heck reaction is still underdeveloped owing to the competitive side reactions of alkyl-palladium species. Herein, we describe the development of a deaminative alkyl-Heck-type reaction that proceeds through C-N bond activation by visible-light photoredox catalysis. A variety of aliphatic primary amines were found to be efficient starting materials for this new process, affording the corresponding alkene products in good yields under mild reaction conditions. Moreover, this strategy was successfully applied to deaminative carbonylative alkyl-Heck-type reactions., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Visible-light photocatalysis is a rapidly developing and powerful strategy to initiate organic transformations, as it closely adheres to the tenants of green and sustainable chemistry. Generally, most visible-light-induced photochemical reactions occur through single-electron transfer (SET) pathways. Recently, visible-light-induced energy-transfer (EnT) reactions have received considerable attentions from the synthetic community as this strategy provides a distinct reaction pathway, and remarkable achievements have been made in this field. In this Review, we highlight the most recent advances in visible-light-induced EnT reactions., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Neutral eosin Y-derived photoexcited states have been found to serve as photoacids and direct hydrogen atom transfer (HAT) catalysts in the activation of glycals and C-H bonds, respectively. These studies pave the way for further use of eosin Y in photochemical synthesis., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A visible-light-driven, copper-catalyzed three-component radical cross-coupling of oxime esters, styrenes, and boronic acids has been developed. Key steps of this protocol involve catalytic generation of an iminyl radical from a redox-active oxime ester and subsequent C-C bond cleavage to generate a cyanoalkyl radical. Upon its addition to styrene, the newly formed benzylic radical undergoes coupling with a boronic-acid-derived ArCu II complex to achieve 1,1-diarylmethane-containing alkylnitriles., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new synergistic multicatalytic activation mode of eosin Y has been discovered by exploiting the redox potential of its ground state and excited state. This catalytic strategy proves to be an enabling tool for visible-light-driven sequential benzylic C-H amination and oxidation of o-benzyl-N-methoxyl-benzamides when using Selectfluor as a hydrogen atom transfer (HAT) reagent and O 2 as oxidant. Efficient synthesis of a range of diversely functionalized 3-hydroxyisoindolinones can thus be achieved with good yields and selectivity at mild reaction conditions. Preliminary mechanistic studies and DFT calculations suggest that eosin Y works as a redox catalyst and photosensitizer., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Palladium-catalyzed allylic substitution reactions have become established as an important tool for the construction of carbon-carbon and carbon-heteroatom bonds in modern organic synthesis. However, controlling the regioselectivity of this type of transformation to afford chiral branched products, in addition to controlling the enantioselectivity, is a significant challenge. Excitingly, controlling nonbonding interactions between the substituents on the π-allyl-palladium intermediate and the nucleophile or palladium catalyst has been shown to be effective in achieving this goal. This Focus Review highlights representative advances in this field, according to the mode of non-bonding interaction, including hydrogen-bonding, electrostatic, and coordination interactions., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A copper-catalyzed regio-reversed asymmetric [3+2] cycloaddition of iminoesters with nitroolefins is disclosed for the first time. This method enables the facile synthesis of polysubstituted chiral pyrrolidines bearing at least one chiral quaternary center in high yields with excellent regio-, diastereo-, and enantioselectivity. The application of chiral P,S ligands and the unique effect of α-aryl groups on the iminoesters are key to the success of this method. The practicality and versatility of the reaction are also demonstrated., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In contrast to the plethora of catalytic systems that enable access to any enantiomers of the chiral products by simply choosing between a pair of enantiomeric or pseudoenantiomeric chiral catalysts, few analogously effective protocols exist for the synthesis of compounds bearing multiple stereogenic centers with full control of the absolute and relative stereochemical configurations. Here, we report the application of our previously developed modular phosphoramidite-thioether ligands for the copper-catalyzed diastereodivergent asymmetric 1,3-dipolar cycloaddition of azomethine ylides and nitroalkenes. Our catalytic system enables wide substrate scope, great stereochemical control, and high reaction efficiency., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A room-temperature, visible-light-driven N-centered iminyl radical-mediated and redox-neutral C-C single bond cleavage/radical addition cascade reaction of oxime esters and unsaturated systems has been accomplished. The strategy tolerates a wide range of O-acyl oximes and unsaturated systems, such as alkenes, silyl enol ethers, alkynes, and isonitrile, enabling highly selective formation of various chemical bonds. This method thus provides an efficient approach to various diversely substituted cyano-containing alkenes, ketones, carbocycles, and heterocycles., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A visible-light-driven radical-mediated strategy for the in situ generation of aza-ortho-quinone methides from 2-vinyl-substituted anilines and alkyl radical precursors is described. This process enables an efficient multicomponent reaction of 2-vinylanilines, halides, and sulfur ylides, and has a wide substrate scope and good functional group tolerance. Treatment of the cycloaddition products with a base leads to densely functionalized indoles in a single-flask operation., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Remote control: New strategies for the activation of remote C(sp 3 )-H bonds by photoredox-catalyzed (PC) radical translocation via O- and N-centered radicals have recently been described. These methods enable the controlled and site-selective functionalization of inert C(sp 3 )-H bonds and provide new opportunities for reaction design (HAT=hydrogen atom transfer)., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A copper-catalyzed decarboxylative amination/hydroamination sequence of propargylic carbamates with various nucleophiles is described for the first time. It features an earth-abundant metal catalyst, mild reaction conditions, and high efficiency. Further treatments of the resultant key intermediates using an acid or a base in one pot enable the controllable and divergent synthesis of two types of functionalized indoles. Moreover, experiments to demonstrate the synthetic potential of this methodology are performed., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A cooperative TEMPO and photoredox catalytic strategy was applied for the first time to the direct conversion of N-H and O-H bonds into N- and O-centred radicals, enabling a general and selective oxidative radical oxyamination and dioxygenation of various β,γ-unsaturated hydrazones and oximes. In the reaction, O2 was employed not only as a terminal oxidant but also as the oxygen source. This protocol provided efficient access to the synthesis of various synthetically and biologically important pyrazoline, pyridazine and isoxazoline derivatives under metal-free and mild reaction conditions. Mechanistic studies revealed that the cooperative organophotocatalytic system functions through two single-electron-transfer (SET) processes., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Bicarbonyl-substituted sulfur ylide is a useful, but inert reagent in organic synthesis. Usually, harsh reaction conditions are required for its transformation. For the first time, it was demonstrated that a new, visible-light photoredox catalytic annulation of sulfur ylides under extremely mild conditions, permits the synthesis of oxindole derivatives in high selectivities and efficiencies. The key to its success is the photocatalytic single-electron-transfer (SET) oxidation of the inert amide and acyl-stabilized sulfur ylides to reactive radical cations, which easily proceeds with intramolecular C-H functionalization to give the final products., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A convergent and highly stereoselective [4+2] cycloaddition of in situ-generated ortho-Quinone methides (o-QMs) and azlactone enols has been successfully developed through a triple Brønsted acid catalysis strategy. This protocol provides an efficient and mild access to various densely functionalized dihydrocoumarins bearing adjacent quaternary and tertiary stereogenic centers in high yields with excellent diastereo- and enantioselectivity., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A catalytic asymmetric [3+2] cycloaddition reaction of chiral palladium-containing N(1) -1,3-dipoles with methyleneindolinones has been successfully developed. The reaction allows an efficient construction of 3,3'-pyrrolinyl spirooxindoles with high yields and excellent stereoselectivities (up to 93 % yield, 19:1 d.r. and >99 % ee). A synthetic application of this methodology is demonstrated and a stereocontrol mechanism is proposed., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The first example of iron-catalyzed decarboxylative (4+1) cycloaddition reactions is described in this publication. By using this method, a wide range of functionalized indoline products were prepared from easily available vinyl benzoxazinanones and sulfur ylides in high yields and selectivities. A possible reaction pathway involving an allylic iron intermediate is discussed based on a series of control experiments and density-functional theory calculations., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new hybrid P,S ligand was exploited by combining a chiral β-amino sulfide and a simple diphenyl phosphite. The resultant ligand performs extremely well in a palladium-catalyzed asymmetric decarboxylative [4+2] cycloaddition reaction, thus generating multiple contiguous stereocenters and a chiral quaternary center. By doing so, a straightforward route to highly functionalized tetrahydroquinolines was developed with yields of up to 99 %, as well as 98 % ee and greater than 95:5 d.r. Moreover, mechanistic insights into this transformation and the possible stereocontrol are discussed., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Visible-light-induced radical decarboxylative functionalization of carboxylic acids and their derivatives has recently received considerable attention as a novel and efficient method to create CC and CX bonds. Generally, this visible-light-promoted decarboxylation process can smoothly occur under mild reaction conditions with a broad range of substrates and an excellent functional-group tolerance. The radical species formed from the decarboxylation step can participate in not only single photocatalytic transformations, but also dual-catalytic cross-coupling reactions by combining photoredox catalysis with other catalytic processes. Recent advances in this research area are discussed herein., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Photocatalysis enables the cascade reactions of indoles and CBr4 in MeOH through a C(sp(2) )H functionalization/methanolysis sequence. The title reaction provides an efficient access to indole 2- and 3-carboxylates in a single operation (no preinstallation of protecting as well as directing groups was required) with good yields under mild reaction conditions., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Visible-light-induced photocatalytic decarboxylative alkynylations of carboxylic acids have been developed for the first time. The reaction features extremely mild conditions, broad substrate scope, and avoids additional oxidants. Importantly, a decarboxylative carbonylative alkynylation has also been carried out in the presence of carbon monoxide (CO) under photocatalytic conditions, which affords valuable ynones in high yields at room temperature., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel and efficient C-P bond formation reaction of diarylphosphine oxides with aryl iodides was achieved by combining nickel catalysis and visible-light-induced photoredox catalysis. This dual-catalytic reaction showed a broad substrate scope, excellent functional group tolerance, and afforded the corresponding products in good to excellent yields. Compared with the previously reported use of photoredox/nickel dual catalysis in the construction of C-C bonds, the methodology described herein was observed to be the first to allow for C-heteroatom bond formation., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The first radical alkoxycarboxylation of aryldiazonium salts using CO gas through visible-light-induced photoredox catalysis (16 W blue LEDs) has been developed. This reaction is entirely metal-free, is carried out at room temperature with a low loading of an organic dye as a photocatalyst (0.5 mol %), and provides a wide range of arylcarboxylic acid esters in high yields. Importantly, this photocatalytic system can be successfully extended to other carboxylation reactions., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An unprecedented α-allylation of amines was achieved by combining palladium catalysis and visible-light photoredox catalysis. In this dual catalysis process, the catalytic generation of allyl radical from the corresponding π-allylpalladium intermediate was achieved without additional metal reducing reagents (redox-neutral). Various allylation products of amines were obtained in high yields through radical cross-coupling under mild reaction conditions. Moreover, the transformation was applied to the formal synthesis of 8-oxoprotoberberine derivatives which show potential anticancer properties., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An unprecedented phototandem catalysis based on a single iridium photocatalyst has been successfully developed. This powerful strategy consists of two mechanistically distinct catalytic cycles, namely, photocatalytic energy transfer (ET) and single electron transfer (SET). The novel protocol allows a rapid and efficient construction of biologically and synthetically important 3-ester-3-hydroxy-2-oxindole derivatives from readily available diazoamides through a cyclization/aerobic oxidation sequence under very mild conditions., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A visible-light photocatalytic generation of N-centered hydrazonyl radicals has been accomplished for the first time. This approach allows efficient intramolecular addition of hydrazonyl radical to terminal alkenes, thus providing hydroamination and oxyamination products in good yields. Importantly, the protocol involves deprotonation of an N-H bond and photocatalytic oxidation to an N-centered radical, thus obviating the need to prepare photolabile amine precursors or the stoichiometric use of oxidizing reagents.

A visible-light-induced photocatalytic aerobic oxidation/[3+2] cycloaddition/aromatization cascade between secondary amines and isocyanides has been successfully developed. The reaction provides a general and efficient access to diversely substituted imidazoles and imidazo[1,5-a]quinoxalin-4(5 H)-ones in good yields under mild conditions., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A photocatalytic formal [3+2] cycloaddition of 2H-azirines with alkynes has been achieved under irradiation by visible light in the presence of organic dye photocatalysts. This transformation provides efficient access to highly functionalized pyrroles in good yields and has been applied to the synthesis of drug analogues. A primary trial of photocascade catalysis merging energy transfer and redox neutral reactions was shown to be successful., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

New players in town: In situ generated transition-metal-containing carbonyl ylides are a unique class of reagents which have found wide applications in catalytic asymmetric cascade reactions. Recent advances in reaction design are likely to lead to more novel developments with these reactive species., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An unprecedented Zn(OTf)2-catalyzed asymmetric Michael addition/cyclization cascade of 3-nitro-2H-chromenes with 3-isothiocyanato oxindoles has been disclosed. This transformation provides an efficient access to various synthetically important polycyclic spirooxindoles in a highly stereoselective manner under mild conditions (72–99% yields, up to >95:5 d.r. and >99% ee). The reaction leads to the formation of three consecutive stereocenters, including 1,3-nonadjacent tetrasubstituted carbon stereocenters, in a single operation. A bifunctional activation model of the chiral Zn(OTf)2/bis(oxazoline) complex was proposed based on control experiments, wherein the ZnII moiety serves as a Lewis acid and the N atom of the free NH group acts as a Lewis base by a hydrogen-bonding interaction.