A Brønsted acid-catalyzed three-component modular phosphonylation/cyclization protocol has been established for the efficient synthesis of phosphinylated 2H-isoindoles, employing o-propargyl alcohol benzaldehydes, diarylphosphine oxides, and arylamines as starting materials. This metal-free cascade transformation is characterized by mild conditions, broad substrate compatibility, gram-scale synthesis, and one-pot construction of C-P, C-N, and CC bonds. Mechanistic studies revealed that this chemistry involves Kabachnik-Fields reaction, 5-exo-dig cyclization, and aromatization. Interestingly, these isoindole-substituted phosphine oxides emit bright fluorescence in the aggregated states under UV irradiation.

A novel cascade phosphorylation/cyclization of indole-containing propargylic alcohols with P(O)-H species under mild conditions is described. This strategy provides an efficient and practical approach to obtaining various valuable 6-phosphoryl-6-vinyl indeno[2,1-b]indoles via the construction of one C-P bond and one C-C bond in a single procedure. This reaction proceeded via a phosphorylated allene initiating the subsequent highly regioselective 5-exo-trig cyclization to afford the target products, which first demonstrates the cyclization as a new reaction mode compared with conventional cyclization pathways.

A highly efficient method for the straightforward synthesis of skipped 1,4-dienes is presented via p-TsOH·H2O-catalyzed intramolecular intercepted Meyer-Schuster rearrangement/allylic alkenylation of propynolaldehydes with olefins in a one-pot manner. This cascade transformation is characterized by metal-free and mild conditions, extensive substrate applicability, atom economy, gram-scale production, and water as the sole by-product. Furthermore, the resulting functionalized 1,4-dienes could be derivatized by Fe(III)-promoted radical cyclization, allylic methoxylation under reductive conditions, and Pd(II)-catalyzed Sonogashira coupling.

Herein we report a novel, efficient gold-catalyzed tandem reaction of alkynols with TMSN3 as a nitrogen source to yield alkenylnitrile derivatives in the presence of TFA. The reaction proceeds under mild conditions and exhibits broad functional group tolerance. The synthetic utility of this reaction has been reflected by its applicability to a wide range of alkynol substrates.

Investigating organic reactions to synthesize novel molecules that exhibit aggregation-induced emission (AIE) characteristics is becoming a research hotspot. Herein, we develop a one-pot phosphinylation/cyclization reaction between propynolaldehydes and diarylphosphine oxides to generate isobenzofuran-substituted phosphine oxides (IBFPOs) displaying AIE properties. Such a reaction possesses benefits such as metal-free synthesis, simple operation and wide substrate applicability. Further structural modifications of the products have been implemented through the palladium-catalyzed Sonogashira reaction, Ullmann coupling and Diels-Alder addition. Furthermore, these AIE luminogens (AIEgens), which have satisfactory quantum yields and tunable emission covering the entire visible region, can be employed for the cell imaging of lipid droplets in HeLa cells. Notably, quantitative evaluation of the phototherapy effect demonstrates that one of these presented AIEgens, namely IBFPO-3j, displays high type-I reactive oxygen species (ROS) generation efficiency, enabling its effective application in photodynamic therapy in a hypoxic environment.

A novel Pd-catalyzed three-component domino reaction for the stereoselective synthesis of highly functionalized allyl cinnamates has been developed. In this protocol, a sequential process of C-C bond activation and intermolecular allylic substitution was well-organized. The key for this transformation is the in situ generated hydrolysis product of cyclopropenone, which triggered a new reaction with vinylethylene carbonates. The reaction mechanism was investigated, demonstrating the high stereoselectivity and excellent atomic economy in this process.

A metal-free and atom-economic route for the synthesis of naphtho-[1,2-b]-furan-3-ones has been realized via p-TsOH center dot H2O-catalyzed intramolecular tandem double cyclization of gamma-hydroxy acetylenic ketones with alkynes in formic acid. The benzene-linked furanonyl-ynes are the key intermediates obtained by the scission/recombination of C-O double bonds. Further, the structural modifications of the representative product were implemented by reduction, demethylation, substitution, and [5 + 2]-cycloaddition.

Aggregation-induced emission luminogens (AIEgens) have gained significant attention in science and manufacture due to its potential application in photoelectric materials and biomedical materials. Thus, development of new organic reactions to synthesize novel AIEgens is highly essential. Due to their unique electronic structures and distinctive optoelectronic properties, the formation of main group heterocycle-based AIEgens is becoming a research hotspot. Herein, we develop a one-pot metal-free Pudovik addition/cyclization/aromatization reaction between o-propargyl alcohol benzaldehydes and diarylphosphine oxides to generate isobenzofuran-based AIEgens. Such reaction possesses green synthesis, simple operation, high skeletal stability, satisfactory quantum yields and tunable emission covering the entire visible region. Moreover, these isobenzofuran-substituted phosphine oxides (IBFPO) can be used as bioprobes for cell imaging of lipid droplets in HeLa cells. Notably, quantitative evaluation of phototherapy effect demonstrates that one of these presented AIEgens, namely IBFPO-3j, displays high Type-I reactive oxygen species (ROS) generation efficiency, enabling its effective application for photodynamic therapy in hypoxic environment. Benefiting from the easy preparation and the tunable emission, versatile IBFPO-based AIEgens provide a new platform toward advanced materials for extensive applications in biological systems.

An efficient and facile strategy for the synthesis of 6-(sulfonylmethyl)phenanthridines and its derivatives has been developed via tandem sulfonylation cyclization of vinyl azides under mild conditions in the absence of any catalysts and additives. The reaction simply utilizes easily accessible and cheap K2S2O5 as the sulfur dioxide source, delivering functionalized phenanthridines in moderate to excellent yields with operational simplicity and gram-scale synthesis, as well as good functional-group tolerance.

A one-pot step-economic tandem process involving (5 + 2)-cycloaddition and Nazarov cyclization reactions has been reported for the facile synthesis of indanone-fused benzo[cd]azulenes from (E)-2-arylidene-3-hydroxyindanones and conjugated eneynes. This highly regio- and stereoselective bisannulation reaction is enabled by dual silver and Brønsted acid catalysis and opens up a new avenue for the construction of important bicyclo[5.3.0]decane skeletons.

An efficient and novel strategy for the synthesis of phosphoric esters has been developed via visible-light-promoted tandem oxyphosphorylation etherification of alpha-diazoesters under mild conditions in the absence of any catalysts and additives. The reaction simply utilizes air (O-2) as the environmentally friendly and sustainable oxygen source, delivering functionalized phosphoric esters in moderate to excellent yield with operational simplicity and gram-scale synthesis, as well as good functional-group tolerance.

The visible-light-mediated tandem phosphorylation/cyclization of N-arylacrylamides with H-phosphine oxides has been developed for the synthesis of phosphorylated oxindoles. This efficient and facile process was useful for the construction of a C-P bond and triggered the formation of a C-C bond with good compatibility with functional groups undermild reaction conditions.

在N-甲基吡咯烷酮的促进下,肉桂酸与草酰氯在10℃酰氯化反应1 h后,再与加入的胺在35℃酰胺化反应4 h得到目标化合物N-肉桂酰胺;目标化合物结构经1H NMR、13C NMR,IR和EI-MS等表征;同时提出了NMP促进反应的可能机理.该方法具有反应条件温和、操作简便和反应时间短等优点.

An efficient and facile visible-light-mediated tandem difluoromethylation/cyclization of alkenyl aldehydes, with easily accessible and air-stable [Ph3PCF2H]+Br- as the difluoromethylation reagent, has been established. A range of CF2H-substituted chroman-4-one skeletons and their derivatives, such as 2,3-dihydroquinolin-4(1H)-ones, chroman, 3,4-dihydronaphthalen-1(2H)-one, 2,3-dihydrobenzofuran, and 2,3-dihydro-1H-inden-1-one, are efficiently produced in moderate to good yields with excellent chemoselectivity under mild reaction conditions.

The aluminum(III) triflate catalyzed three-component coupling reaction of alkynes, amines and phosphorylated aryl aldehydes to access phosphoryl quinoline derivatives has been developed. The reaction proceeds in a simple system without the use of transition metals, ligands or additives, thus making it attractive for the fast preparation of a variety of new potential N-P bidentate ligands.

γ‐Lycorane, a degradation product of the Aromaticaceae alkaloid lycorine, is one of the most attractive molecules in the Aromaticaceae family. It remains a popular target for synthesis due to its pentacyclic structure, which presents a vehicle for demonstrating the utility of new synthetic strategies. Various synthetic methods have been developed by synthetic chemists since the first synthesis of γ‐lycorane by Nasuo in 1966. Thus, this review presents an overview of the literature on the ways utilized within the synthesis of γ‐lycorane in racemic and enantiopure forms via electrophilic arylation, Pd‐catalyzed C−C coupling, Bischler–Napieralski cyclization, Pictet–Spengler cyclization, photocyclization, radical cyclization, chiral pool synthesis, chiral auxiliary‐mediated synthesis, and catalytic asymmetric synthesis, ranging from 1966 to 2022.

This review summaries a view of the advances in the direct transformation of propargylic alcohols to functionalized allenes.

含sp3 C-P键化合物是一类重要的化学原料和有机合成中间体.近年来,通过过渡金属催化sp3 C-H键活化反应来构筑sp3 C-P键受到了广泛关注并取得了显著的发展.根据不同的过渡金属催化剂进行分类,对近年来过渡金属催化sp3 C-H键活化构筑sp3 C-P键反应进行了综述,并对该研究领域的局限性和未来发展前景进行总结和展望.