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Background: The current study aimed to investigate the sleep quality of patients after valve replacement surgery due to infective endocarditis and identify risk factors for disturbed sleep post hospitalisation. Methods: Eighty patients were assessed postoperatively using subjective scale measures, the Pittsburgh sleep quality index (PSQI) and the Epworth sleepiness scale, and an objective measure, actigraphy. Scale measures were assessed approximately 2 weeks and 6 months after surgery. Actigraphy monitoring was performed for 2 consecutive weeks during hospitalisation. Logistic regression was used to identify risk factors for disturbed sleep. Results: The study population (n = 80) had an average age of 42.8 ± 14.2 years, and 67.5% were male. The median sleep efficiency was 85.3% in week 1 and 86.8% in week 2. The frequency of awakenings was significantly higher in week 1 (20.0 times vs. 19.3 times, p = 0.017). The scale measures showed significant improvement in sleep by 6 months after surgery compared to that during hospitalisation. Multivariable logistic regression analysis suggested that the possible risk factors for disturbed sleep 6 months after surgery included age (OR = 1.479, 95%CI 1.140–1.920) and a few parameters of early postoperative disturbed sleep quality (PSQI: OR = 2.921, 95%CI 1.431–5.963; sleep efficiency: OR = 0.402, 95%CI 0.206–0.783; and average duration of awakenings: OR = 0.006, 95%CI 0.000–0.827). Conclusions: Disturbed sleep quality was witnessed in postoperative patients during hospitalisation and up to 6 months after surgery. Over time, the patients' sleep quality improved significantly. Age and a few early postoperative sleep quality variables were risk factors for disturbed sleep 6 months after surgery. [ABSTRACT FROM AUTHOR]

A new, general silver-catalyzed oxidative 1,2-alkyletherification of unactivated olefinic ketones with primary, secondary and tertiary α-bromoalkyl carbonyls promoted by tert-butyl hydroperoxide (TBHP) and Et3N has been developed. Through the cooperative action of Ag2O, TBHP and Et3N, the reaction enables the construction of highly valuable quaternary-carbon-possessing 2,3-dihydrofuran frameworks using a concomitant intramolecular annulation strategy. [ABSTRACT FROM AUTHOR]

Abstract: C−N bonds are widely found in natural products, medicinal molecules and multifunctional materials. In recent years, the construction of C−N bonds through a radical coupling reaction between carbon‐centered radicals with nitrogen‐centered radicals has emerged as a frontier area in organic chemistry. This review summarizes the recent advances (especially those after 2012) in radical coupling reactions that facilitate the formation of C−N bonds. The main achievements on this area are presented according to the pattern of the nitrogen‐centered radicals generated. Selected examples of substrates are listed and special attention is paid to the reaction mechanisms. Moreover, a personal outlook is described at the end. [ABSTRACT FROM AUTHOR]

A metal-free nitration of the C( sp3)−H bonds of 2-oxindoles with t-BuONO through radical coupling reaction at room temperature has been developed. Using t-BuONO both as a nitrating reagent and as an oxidant, to couple with the C( sp3)−H bonds of 2-oxindoles, thus forming a new C−N bond without using any other reagents. This reaction provides a green and straightforward approach to some useful 3-nitro-2-oxindoles in moderate to good yields. [ABSTRACT FROM AUTHOR]

A new copper-catalyzed oxidative difunctionalization of enol ethers with α-amino carbonyl compounds and hydroperoxides is developed. This method is experimentally simple while allowing for regioselective access to 2-amino-3,4-dioxy carbonyl compounds in good yields, and represents the first example of alkene oxyalkylation through C(sp3)–H functionalization. [ABSTRACT FROM AUTHOR]

A new transition metal-free oxidative coupling of unactivated terminal alkenes with aldehydes and hydroperoxides in the presence of 10 mol% potassium tert-butanolate ( t-BuOK) is described thereby realizing trifunctionalization of alkenes toward 2,3-epoxy ketones. This method is applicable to a wide range of aldehydes, including aryl and alkyl aldehydes, with excellent functional group tolerance, and provides for the one-step assembly of 2,3-epoxy ketones. [ABSTRACT FROM AUTHOR]

The oxidative interception of various σ-alkyl palladium(II) intermediates with additional reagents for the difunctionalization of alkenes is an important research area. A new palladium-catalyzed oxidative difunctionalization reaction of alkenes with α-carbonyl alkyl bromides is described, in which the σ-alkyl palladium(II) intermediate is generated through a Heck insertion and trapped using an aryl C(sp2)H bond. This method can be applied to various α-carbonyl alkyl bromides, including primary, secondary, and tertiary α-bromoalkyl esters, ketones, and amides. [ABSTRACT FROM AUTHOR]

A novel copper-catalyzed oxidative alkylation of α-amino carbonyl compounds with ethers has been established for the selective synthesis of α-etherized α-amino carbonyl compounds. This oxidative alkylation is achieved by dual C( sp3)H bond oxidative cross-coupling, and its scope is expanded to α-amino ketones, α-amino esters and α-amino amides. [ABSTRACT FROM AUTHOR]

Difunctionalization: Inexpensive and environmentally benign FeCl3 catalyzes the oxidative 1,2‐alkylarylation of activated alkenes with an aryl C(sp2)H bond and a C(sp3)H bond adjacent to a heteroatom. This reaction is a new strategy for the synthesis of oxindoles and makes use of DBU as ligand and TBHP as oxidant (see scheme, TBHP=tert‐butyl hydrogenperoxide). [ABSTRACT FROM AUTHOR]

Difunktionalisierung: Preiswertes und umweltschonendes FeCl3 katalysiert die oxidative 1,2 ‐ Alkylarylierung aktivierter Alkene zu Verbindungen mit einer Aryl ‐ C(sp2) ‐ H ‐ und einer C(sp3) ‐ H ‐ Bindung in Nachbarschaft zu einem Heteroatom. Die Reaktion nutzt DBU als Liganden und TBHP als Oxidationsmittel und bietet eine neue Strategie für die Synthese von Oxindolen (siehe Schema, TBHP=tert ‐ Butylhydroperoxid). [ABSTRACT FROM AUTHOR]

A novel gold-catalyzed skeletal rearrangement of 1-[2- (1H-isochromen-3-yl)aryl]ethanones with alcohols to construct a five-membered carbocycle ring onto aromatic systems has been developed. This method serves as the first example of synthesizing inden- 1-ones by a gold-catalyzed skeletal rearrangement strategy. [ABSTRACT FROM AUTHOR]

Royal jelly is one of the most important products of honeybees. Given its role in development of bee brood into fertile individuals of the royal caste it is also used in health products for human consumption. Royal jelly spoils and loses its health-promoting properties depending on storage duration and conditions. To ensure product quality before selling, it is therefore necessary to assess royal jelly freshness. Many indexes of freshness have been suggested, but they all lack reliability or require complex and time-consuming analyses. Here we describe a method to detect royal jelly freshness based on a chromogenic reaction between royal jelly and HCl. We demonstrate that analyses based on color parameters allow for the discrimination of royal jelly samples based on the duration of their storage. Color parameters of royal jelly stored at −18 and 4 °C for 28 d remained comparable to that of fresh samples, which supports the reliability of the method. The method of freshness determination described is practical, cheap, and fast and can thus be used in real-time when trading royal jelly. Practical Application: The method developed can be used to assess royal jelly freshness. It is practical, cheap, and fast and can thus be used in real-time when trading royal jelly. [ABSTRACT FROM AUTHOR]

Vinyl sulfones are important structural motifs with a wide range of applications in the biomedical field. Although the hydrosulfonylations of alkynes have provided straightforward strategies for the synthesis of vinyl sulfones, these methods still exhibit several drawbacks, such as the use of large amounts of transition metal catalysts or/and additional additives. Herein, we report an efficient and mild multicomponent reaction (MCR) for the preparation of vinyl sulfones achieved by carrying out hydrosulfonylation of alkynes with the corresponding aryl diazonium salts, K2S2O5 and thiophenols at room temperature without any metal catalysts or additives. This transformation was the first example of a thiophenol as a hydrogen source reacting with vinyl radical with the advantages of high chemoselectivity and step-economy. Notably, the method was found to also be applicable to aliphatic alkynes, circumventing the limitations of existing methods, and a gram-scale experiment proceeded smoothly, proving the practicality of the methodology. [ABSTRACT FROM AUTHOR]

Difunctionalization of alkenes allows the rapid construction of complex molecules with high selectivity and efficiency in organic synthesis. Herein, we first describe a 1,2‐hydroxycarbonylation of alkenes for the preparation of hydroxyl‐functionalized chroman‐4‐ones through the cooperative action of inorganic oxidants and organic acids. The transformation is initiated by the formation of an acyl radical, and then experiences intramolecular 6‐exo‐trig radical cyclization and hydroxylation process. It is notable that the hydroxyl group in the final products originate from organic acids without the use of any transition‐metal catalysts. To further demonstrate the practicality and mechanism of this method, the gram‐scale reaction and a series of control experiments including gas chromatography‐mass spectrometry (GC‐MS) and infrared (IR) absorption spectroscopy experiments were performed, and the corresponding intermediates were successfully captured. [ABSTRACT FROM AUTHOR]

The synergistic systems of photoredox and copper catalyst have already appeared as a novel formation of green synthetic chemistry, which open new avenues for chemical synthesis applications. We describe a novel strategy for the cyclization of alkyne‐tethered α‐bromocarbonyls initiated by the cleavage of C(sp3)−Br bond via the collaboration of photoredox and copper catalyst. The present protocol exhibits mildness using economical copper catalyst and visible‐light at room temperature. The gram‐scale and sunlight irradiation experiments proceeded smoothly to show the practicality of the methodology. It is notable that the newly generated oxygen in the product originates from H2O. [ABSTRACT FROM AUTHOR]

Chemodivergent tandem radical cyclization offers exciting possibilities for the synthesis of structurally diverse cyclic compounds. Herein, we revealed a chemodivergent tandem cyclization of alkene‐substituted quinazolinones under metal‐ and base‐free conditions, this transformation is initiated by alkyl radicals produced from oxidant‐induced α‐C(sp3)−H functionalization of alkyl nitriles or esters. The reaction resulted in the selective synthesis of a series of mono‐ and di‐alkylated ring‐fused quinazolinones by modulating the loading of oxidant, reaction temperature, and reaction time. Mechanistic investigations show that the mono‐alkylated ring‐fused quinazolinones is constructed by the key process of 1,2‐hydrogen shift, whereas the di‐alkylated ring‐fused quinazolinones is mainly achieved through crucial steps of resonance and proton transfer. This protocol is the first example of remote second alkylation on the aromatic ring via α‐C(sp3)−H functionalization and difunctionalization achieved by association of two unsaturated bonds in radical cyclization. [ABSTRACT FROM AUTHOR]

A new palladium-catalyzed oxidative difunctionalization reaction of N-arylalkenes with primary, secondary, and tertiary α-carbonyl alkyl bromides affording indolinones is presented. The reaction is initiated by a Heck insertion and requires the addition of Ag2CO3. This transformation includes tandem C--Br/C--H functionalization and cyclization steps that occur through an oxidative radical pathway. [ABSTRACT FROM AUTHOR]

A novel 5-exo-dig/6-endo-trig bicyclization of 1,6-enynes with sulfonyl hydrazides in the aqueous phase using the cheap and available tetrabutylammonium iodide (TBAI)–tert-butyl hydroperoxide (TBHP) combined system is reported. The resulting reaction of diverse nitrogen- and oxygen-polyheterocycles displays high chemical selectivity, high step-economy, and a moderate substrate scope. Moreover, iodosulfonylation can be realized by modulating the structure of the 1,6-enynes. [ABSTRACT FROM AUTHOR]

leading to 2-amino-3,4-dioxy carbonyl compounds in moderate to good yields [ABSTRACT FROM AUTHOR]

2,3-Epoxy ketones [(III) and (V)] are synthesized through an oxidative radical pathway with a broad substrate scope and excellent selectivity control. [ABSTRACT FROM AUTHOR]

Mono- and difunctionalization of a broad scope of non-activated alkenes is achieved with excellent chemoselectivities by a new oxidative coupling method. [ABSTRACT FROM AUTHOR]

A convenient and straightforward approach for the radical cascade cyclization/hydrolysis of CN‐containing 1,6‐enynes with simple ethers under metal‐ and base‐free conditions is described. This strategy provides a variety of valuable ethers‐substituted polyheterocycles via the construction of three C−C bonds, one C=O bond, and two new six‐membered rings within a single procedure. The resulting products can smoothly undergo follow‐up conversions to various useful scaffolds. The methodology shows excellent functional group tolerance, high step‐ and atom‐ economy, and mild reaction conditions, which can be further scaled up to gram quantity in a satisfactory yield. [ABSTRACT FROM AUTHOR]

An abstract of the article "Synthesis of Oxindoles by Iron-Catalyzed Oxidatives 1,2-Alkylarylation of Activated Alkenes with an Aryl C(sp2)-H Bond and a C(sp3)-H Bond Adjacent to a Heteroatom" by Wen-Ting Wei, Ming-Bo Zhou, and Jian-Hong Fan is presented.

We describe a photocatalytic decarboxylative cyclization of 1,6-enynes or N -methacryloyl-2-phenylbenzimidazoles for efficient and ecofriendly syntheses of lactams or benzimidazo[2,1- a ]isoquinoline-6(5 H)-ones, respectively, by the use of KI/PPh3 as a redox catalyst system. In this method, N -hydroxyphthalimide esters were used as alkyl-radical precursors to achieve this decarboxylative cyclization without any dyes, transition-metal catalysts, oxidants, or bases. [ABSTRACT FROM AUTHOR]

A novel method for assembling pyrrolidine-2,4-diones from 1,5-enenitriles and acetone/acetonitrile via a cyclization/hydrolysis has been established under metal-catalyst- and base-free conditions, with Oxone as a green oxidant and H2 O as an additive at 90–110 ℃. This strategy is highlighted by cyclization/hydrolysis of alkyl cyanides, achieving direct C(sp3)–H oxidative functionalization, and giving full conversion of the substrates with excellent functional group compatibility. [ABSTRACT FROM AUTHOR]

A method for radical cyclization of N -methacryloyl-2-arylbenzoimidazoles with nitriles, ketones, and tert -butyl nitrite (TBN) for the preparation of benzimidazo[2,1- a ]isoquinolin-6(5 H)-ones with the advantage of mild reaction conditions, excellent functional group compatibility, and broad substrate scope is reported. The present strategy has favorable characteristics: (1) the use of cheap metal catalysis; (2) N -radical-initiated cyclization of N -methacryloyl-2-arylbenzoimidazoles; and (3) rare example of radical C(sp3)–H functionalization in this cyclization. [ABSTRACT FROM AUTHOR]

Ring opening/ring closure produces a broad spectrum of indenone derivatives. [ABSTRACT FROM AUTHOR]

Two novel C(sp3)−H functionalization of inert alkanes and visible‐light promoted oxidation decarboxylation of N‐hydroxyphthalimide (NHP) esters to access polycyclic quinazolinones have been described. These methods do not involve metal catalysts and are carried out in water or water/DMSO media. The wide substrate scope, even including the seven‐membered ring under mild reaction conditions, demonstrate the practicability of these strategies. [ABSTRACT FROM AUTHOR]

Here we present a transition‐metal‐free radical cyclization of 2‐arylbenzoimidazoles with unactivated alkanes. By using di‐tert‐butyl peroxide (DTBP) to promote the C(sp3)−H bond functionalization, this approach enables assembly of various benzimidazo[2,1‐a]isoquinolin‐6(5H)‐ones in aqueous media. This strategy can not only well tolerate a wide range of cyclic alkanes, straight‐chain alkanes, toluene derivatives, as well as pharmaceutical molecule eudesmol, but also provides an approach for the functionalization of unactivated C(sp3)−H bonds in aqueous media under transition‐metal‐free systems. [ABSTRACT FROM AUTHOR]

A new method for the nitrative spirocyclization of alkynes is described. This method involves the oxidative difunctionalization of alkynes initiated by a radical attack pathway using t-BuONO ( tert-butyl nitrite) combined with water as the nitro source and TEMPO [(2,2,6,6-tetramethyl-piperidin-1-yl)oxyl] as the initiator, and it represents a new example of oxidative alkyne difunctionalization via the formation of CN/CC bonds for the assembly of nitroalkene unit-containing spirocycles. [ABSTRACT FROM AUTHOR]

2‐Pyrrolidones have aroused enormous interest as a useful structural moiety in drug discovery; however, not only does their syntheses suffer from low selectivity and yield, but also it requires high catalyst loadings. The radical cyclization of 1,n‐enynes and 1,n‐dienes has demonstrated to be an attractive method for the synthesis of 2‐pyrrolidones due to its mild reaction conditions, fewer steps, higher atom economy, excellent functional group compatibility, and high regioselectivity. Furthermore, radical receptors with unsaturated bonds (i. e. 1,n‐enynes and 1,n‐dienes) play a crucial role in realizing radical cyclization because of the ability to selectively introduce one or more radical sources. In this review, we discuss representative examples of methods involving the radical cyclization of 1,n‐enynes and 1,n‐dienes published in the last five years and discuss each prominent reaction design and mechanism, providing favorable tools for the synthesis of valuable 2‐pyrrolidone for a variety of applications. [ABSTRACT FROM AUTHOR]

A novel sulfonyl radical triggered selective iodosulfonylation and bicyclization of 1,6-dienes has been described for the first time. High selectivity and efficiency, mild reaction conditions, excellent functional group compatibility, and broad substrate scope are the attractive features of this synthetic protocol, which provides a unique platform for precise radical cyclization. [ABSTRACT FROM AUTHOR]

Iron-catalyzed oxidative cyclization of olefinic 1,3-dicarbonyls with ketone C(sp3)–H bonds through C–C and C–O bond formations has been described for the first time. A broad substrate scope and ease of scale-up are the attractive features of this synthetic method, which provides a series of potentially bioactive 2,3-dihydrofurans. The reaction pathway is proposed to involve a radical addition of the in situ formed α-carbonyl radical to the C＝C bond of olefinic 1,3-dicarbonyls followed by intramolecular 5-endo-trig cyclization. [ABSTRACT FROM AUTHOR]

Run-Wei Yang, Ying-Yue Zeng and Wen-Ting Wei contributed equally to this work. FOXC2 promotes colorectal cancer proliferation through inhibition of FOXO3a and activation of MAPK and AKT signaling pathways. [Extracted from the article]

Radical-mediated functionalization of alkenes has been emerging as an elegant and straightforward protocol to increase molecule complexity. Moreover, the abstraction of a hydrogen atom from aldehydes to afford acyl radicals has evolved as a rising star due to its high atom-economy and the ready availability of aldehydes. Considering the great influence and synthetic potential of acyl radical enabled reactions between aldehydes and alkenes, we provide a summary of the state of the art in this field with a specific emphasis on the working models and corresponding mechanisms. The discussion is divided according to the kind of alkenes and reaction type. [ABSTRACT FROM AUTHOR]

A new, efficient, and practical radical cyclization of olefinic amides with ketones through α-C(sp3)–H functionalization in the presence of tert -butyl peroxybenzoate (TBPB) is described for the first time. This protocol assembles a wide range of pivotal and useful benzoxazines in good to excellent yields under mild, catalyst-free, ligand-free, and base-free conditions with wide functional group tolerance. Moreover, the mechanistic study indicates that the α-carbonyl radical is involved in this transformation. [ABSTRACT FROM AUTHOR]

The construction of C−N bonds is a central tenet of modern synthetic chemistry as it widely exists in bioactive molecules, natural products, and functional materials. Visible‐light induced strategies can serve as particularly powerful tools for achieving C−N bond formation. This mini review summarizes the recent advancements in the transformation of C(sp3)−H bonds into C−N bonds via photocatalysis under metal catalyst‐free conditions. These reactions generally occur in the presence of abundant and clean visible‐light at ambient temperature without the use of metal catalysts, which undoubtedly represents a future trend in green and sustainable chemistry. The main achievements in this area from 2015 until the present are described according to the type of nitrogen sources and emphasis is placed on the working mechanisms. [ABSTRACT FROM AUTHOR]

Without using any additives, a practical and eco-friendly methodology has been realized for the tandem double cyclization of 1,6-dienes with easily accessible azobis(alkylcarbonitriles) on water. This chemistry has mild reaction conditions, employing water as the sole solvent, with high regioselectivity and ease of scale-up. Moreover, this is the first example of 1,n-diene cyclization using azobis(alkylcarbonitriles) as a two-carbon unit for the construction of polycyclic skeletons. [ABSTRACT FROM AUTHOR]

A concise and eco-friendly acylation/cyclization of 1,6-dienes with linear ethers under catalyst- and base-free conditions has been developed. tert-Butyl hydroperoxide (TBHP)-promoted tandem cleavage of C(sp3)–H and C(sp3)–O bonds of linear ethers is the key in this process, which provides a straightforward and efficient method to realize acylation reaction. The significant advantages of this method include catalyst- and base-free, mild reaction conditions, high scalability, operational simplicity, ease of scale-up, dual roles of ethers and controllable synthesis. [ABSTRACT FROM AUTHOR]

Nitrogen‐containing compounds widely exist in pharmaceuticals and multifunctional materials. Thus, the development of C−N bond formation reactions is of great importance in synthetic chemistry. Since 2014, obvious progress has been made in the construction of C−N bonds via metal‐free radical C(sp3)−H functionalization, which is one of the major protocols due to its high reaction activity and mild conditions. To the best of our knowledge, there are still no exclusive reviews about the formation of C−N bonds through metal‐free radical C(sp3)−H functionalization. This review aims to highlight the recent advances in this area since 2014, according to the type of the nitrogen source (amines, amides, sulfonamides, azoles, azides and other nitrogen sources). The paper is focused on discussions about the reaction mechanisms and selected examples of substrates have also been listed. [ABSTRACT FROM AUTHOR]

The development of efficient and mild methods to assemble C–N bonds represents an important and appealing goal in modern synthetic chemistry. Recently, (hetero) aryl C(sp2)–H functionalization involving a radical process has emerged as an ideal and powerful route to construct C–N bonds, along with diminished cost and waste. As a simple and green methodology, photocatalysis offers selective and efficient access to the generation of radical species. This review presents state-of-the-art examples of photochemical strategies for C–N bond formation via metal catalyst-free (hetero) aryl C(sp2)–H functionalization since 2015. The discussion is divided into six sections according to the type of nitrogen sources and emphasis is placed on the related reaction mechanisms. [ABSTRACT FROM AUTHOR]

Nitro compounds serve as valuable intermediates for pharmaceuticals, agrochemicals, dyes, and polymers. In recent years, radical nitration using tert -butyl nitrite (t -BuONO) has attracted wide attention and desirable progress has been made. On the one hand, t -BuONO is a potential active nitro radical source and can react with various functional groups. On the other hand, as a green and novel nitration reagent, t -BuONO has relatively low price and can easily produce a radical under mild conditions, which undoubtedly provides a simple and efficient way for nitration reactions. To date, some important reviews are available that summarize the synthesis of nitro compounds. To the best of our knowledge, however, there is still no review that exclusively discusses the synthesis of nitro compounds using t -BuONO through a radical strategy. Therefore, this review aims to highlight the recent advances in radical nitration using t -BuONO as nitration reagent. The main progress in this area has been presented according to the type of reaction substrates. Special attention has been paid discussion of the reaction mechanisms and selected examples of substrates have been given. We hope this paper will be a useful reference and inspiration for those who are exploring the synthesis of nitro compounds using t -BuONO. 1 Introduction 2 Radical Nitration of Alkenes 3 Radical Nitration of Aromatics 4 Radical Nitration of Alkynes 5 Radical Nitration of 1, n -Enynes 6 Radical Nitration of Alkanes 7 Summary and Perspective [ABSTRACT FROM AUTHOR]

We conjugated aldehyde‐BODIPY with the water‐soluble iodopropionic‐acid‐hemicyanine to develop a new dual‐color fluorescence probe (BHC) for selective and sensitive monitoring of endogenous SO2 for the first time. Through excellent water solubility and the unique nucleophilic addition reaction, BHC has a higher selectivity for the colorimetric monitoring of SO2 than other related substances. The resulting probe BHC has red emission, and can be converted to green emission after reacting with SO2. Then the dual‐color fluorescence probe was further applied to image intracellular endogenous generated SO32−/HSO3− by the metabolism of living cells with satisfactory results. This strategy provides a new tool for revealing the metabolism of SO32−/HSO3− and quantifying their distribution in living cells. [ABSTRACT FROM AUTHOR]

Without employing any photocatalyst and additive, an economical, eco-friendly and practical strategy has been developed for the visible-light-initiated regioselective sulfonylation/cyclization of 1,6-enynes in a biomass-derived green solvent 2-methylTHF from easily accessible sulfonyl chlorides under open-air conditions at room temperature. Compared with conventional heating conditions, the use of a 3 W blue light-emitting diode (LED) or sunlight not only reduces energy consumption but also minimizes side reactions. This transformation has excellent regioselectivity, mild reaction conditions, broad substrate scope and ease of scale-up. Moreover, mechanistic studies indicated that a sulfonyl radical pathway was involved in this reaction. [ABSTRACT FROM AUTHOR]

In this paper, selective cyanoalkylation and [2+2+2] annulation of 1,6‐enynes with azobis(alkylcarbonitriles) under mild conditions is presented. When the reaction was run in EtOAc without any catalysts or additives, a highly regioselective cyanoalkylation of 1,6‐enynes was achieved. On the other hand, when a mixture of H2O and EtOAc was used as the green reaction medium in the presence of a cheap copper catalyst and an additive, a [2+2+2] annulation of 1,6‐enynes with azobis(isobutyronitrile) (AIBN) and H2O occurred to form four new chemical bonds in one step. [ABSTRACT FROM AUTHOR]

Herein we report a protocol for commercial available oxone‐mediated nitration cyclization between 1,6‐enynes and Cu(NO3)2. This strategy shows attractive characteristics such as mild reaction conditions, operational simplicity, broad substrates scope with good to excellent yields and high functional group tolerance. The reaction provides a regioselective way toward the formation of a new C−N and C−C bonds in one step. Mechanistic studies reveal that the procedure undergoes a radical process. [ABSTRACT FROM AUTHOR]

A practical synthetic route to 1,3‐diynes from terminal alkyl alkynes through copper‐catalyzed oxidative coupling is developed. The remarkable features of this oxidative coupling including the base‐ and ligand‐free construct of C−C bond, mild reaction conditions, as well as wide substrate scope that is particularly compatible with some terminal alkyl alkynes. A practical synthetic route to 1,3‐diynes from terminal alkyl alkynes through copper‐catalyzed oxidative coupling is developed. The remarkable features of this oxidative coupling including the base‐ and ligand‐free construct of C−C bond, mild reaction conditions, as well as wide substrate scope that is particularly compatible with some terminal alkyl alkynes. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Economical TBAI/TBHP system. • Water as the sole solvent. • Radical Heck-type coupling reaction. Abstract Herein, metal-free radical Heck-type reaction of styrenes with sulfonyl hydrazides to synthesize vinyl sulfones is developed. The reaction is performed under economical TBAI/TBHP system on water in open air at room temperature, which proceeds through the radical addition to styrenes followed by hydrogen-abstraction. When compared to known approaches for the synthesis of vinyl sulfones from alkenes, this radical Heck-type strategy is practical, green and does not go through HI elimination process. Furthermore, this protocol can be expanded to the iodosulfonylation of alkynes for the synthesis of iodovinyl sulfones. [ABSTRACT FROM AUTHOR]

The Cu-catalyzed oxidative [2+2+1] annulation of 1,n-enynes (n = 6, 7) with α-carbonyl alkyl bromides through C–Br/C–H functionalization has been developed. Using Ag2CO3/tert-butyl hydroperoxide (TBHP) as co-oxidants, α-carbonyl alkyl bromides provide two bonds, the α-C(sp3)–Br bonds and the α-C(sp3)–H bonds, to cyclize with the 1,n-enynes and Cu(MeCN)4PF6, thus forming three new C–C bonds and two rings in a single reaction. [ABSTRACT FROM AUTHOR]

A new protocol for nitrative spirocyclization of alkynes is described. [ABSTRACT FROM AUTHOR]