Recent advances in iron-catalysed coupling reactions for the construction of the C(sp2)-C(sp2) bond.

The advancement of transition-metal-catalyzed coupling reactions has been demonstrated as a highly effective strategy for the formation of carbon-carbon bonds, which serve as the fundamental basis for organic synthetic chemistry. Given that iron represents one of the most economical and ecologically sustainable metallic elements available, the exploration and enhancement of iron-catalysed coupling reactions have garnered increasing interest within the scientific community. In recent years, numerous iron-catalysed reactions have been reported, showcasing their efficacy in establishing C-C bonds. In this minireview, we present a systematic analysis of C(sp2)-C(sp2) bond formation via iron-catalysed coupling reactions as documented in the extant literature.

Sustainable and practical formation of carbon-carbon and carbon-heteroatom bonds employing organo-alkali metal reagents.

Metal-catalysed cross-coupling reactions are amongst the most widely used methods to directly construct new bonds. In this connection, sustainable and practical protocols, especially transition metal-catalysed cross-coupling reactions, have become the focus in many aspects of synthetic chemistry due to their high efficiency and atom economy. This review summarises recent advances from 2012 to 2022 in the formation of carbon-carbon bonds and carbon-heteroatom bonds by employing organo-alkali metal reagents.

Iridium-catalyzed enantioselective alkynylation and kinetic resolution of alkyl allylic alcohols.

Herein, we report an efficient kinetic resolution of alkyl allylic alcohols enabled by an iridium-catalyzed enantioselective alkynylation of alkyl allylic alcohols with potassium alkynyltrifluoroborates. A wide range of chiral 1,4-enynes bearing various functional groups and unreacted enantioenriched allylic alcohols were obtained with excellent enantioselectivities and high kinetic resolution performance (s-factor up to 922). Additionally, this method is particularly effective for preparing some useful optically pure alkyl allylic alcohols, such as the key components towards the synthesis of prostaglandins and naturally occurring matsutakeols, which are difficult to access via other asymmetric reactions. Mechanistic studies revealed that the efficient kinetic resolution might be due to the significant distinction of the η 2-coordination between the (R)- and (S)-allylic alcohols with the iridium/(phosphoramidite, olefin) complex.

Optical resolution of 1,16-dihydroxytetraphenylene by chiral gold(iii) complexation and its applications as chiral ligands in asymmetric catalysis.

We report herein a novel approach involving optical resolution of (±)-1,16-dihydroxytetraphenylene (DHTP) by chiral gold(iii) complexation. This method features several key advantages, i.e., recyclability of chiral resolution reagents, feasibility of scaling up to gram quantities, and operational simplicity. On the basis of this method, which led to optically pure DHTP, a library of 2,15-diaryl (S)-DHTPs and several (S)-DHTP-derived phosphoramidite ligands were synthesized. Finally, the superior performance of a (S)-DHTP phosphoramidite ligand was demonstrated by efficient iridium-catalyzed asymmetric allylic alkynylation reactions.

Palladium-Catalyzed Asymmetric (3 + 2) Cycloaddition of Vinyl Epoxides with Substituted Propiolates. Enantioselective Formation of 2,3,4-Trisubstituted 2,3-Dihydrofurans.

Alkynyl esters are viable dipolarophiles for the palladium-catalyzed asymmetric (3 + 2) cycloaddition with vinyl epoxides. The chiral dihydrofurans are obtained in high yields and high ee values. The use of a chiral benzylic substituted P,N-ligand is essential. The usefulness of the synthetic method has been demonstrated; 2,3-cis-tetrahydrofuran was also provided.

Stereospecific Iron-Catalyzed Carbon (sp2)-Carbon (sp2) Cross-Coupling of Aryllithium with Vinyl Halides.

We present herein an efficient synthetic protocol involving iron-catalyzed cross-coupling of organolithium compounds with vinyl halides as key coupling partners. More than 30 examples were obtained with moderate to good yields and high stereoselectivities. The practicality of this method is evidenced by a gram-scale synthesis. In addition, a preliminary mechanistic investigation was also performed.

Total Synthesis of Cryptotrione.

The total synthesis of cryptotrione (1) was enabled by substrate-controlled diastereoselective construction of the bicyclo[3.1.0]hexene framework through platinum-catalyzed enyne cycloisomerization and Lewis acid induced polyene cyclization to construct the abietane-type tricyclic diterpene skeleton. The stereogenic tertiary carbon center in the side chain was installed in a diastereodivergent manner by conjugate addition reactions.

Visible-Light-Driven Difluoromethylation of Isocyanides with S-(Difluoromethyl)diarylsulfonium Salt: Access to a Wide Variety of Difluoromethylated Phenanthridines and Isoquinolines.

A highly efficient approach of visible-light-driven radical difluoromethylation of isocyanides to access a wide variety of difluoromethylated phenanthridines and isoquinolines is herein described. Electrophilic S-(difluoromethyl)diarylsulfonium salt proved to be a good difluoromethyl radical precursor under photoredox catalysis. A broad range of isocyanides were tolerated to furnish the corresponding difluoromethylated phenanthridines, isoquinolines, furo[3,2-c]pyridine, and pyrido[3,4-b]indole in moderate to excellent yields under mild conditions. A plausible mechanism was also proposed.

Total Syntheses of (-)-Deoxoapodine, (-)-Kopsifoline D, and (-)-Beninine.

The total syntheses of Aspidosperma and Kopsia alkaloids (-)-deoxoapodine, (-)-kopsifoline D, and (-)-beninine are described through a domino deprotection-Michael addition-nucleophilic substitution protocol to assemble the core framework in efficient steps. Corey-Bakshi-Shibata reduction was employed to afford the enantioenriched intermediate for the total syntheses of the aforementioned alkaloids. The chirality was shown to completely transfer to the backbone using Johnson-Claisen rearrangement. The enantioselective total syntheses of (-)-kopsifoline D and (-)-beninine were accomplished for the first time. Our strategy opens up practical avenues for the total synthesis of structurally similar alkaloids.

Difluoromethylation of Phenols and Thiophenols with the S-(Difluo-romethyl)sulfonium Salt: Reaction, Scope, and Mechanistic Study.

A facile and practical approach for the difluoromethylation of phenols and thiophenols was described. Making use of the recently developed bench-stable S-(difluoromethyl)sulfonium salt as the difluorocarbene precursor, a wide variety of diversely functionalized phenols and thiophenols were readily converted to their corresponding aryl difluoromethyl ethers in good to excellent yields in the presence of lithium hydroxide. Chemoselectivity of various O,S-nucleophiles toward difluorocarbene was systematically studied, suggesting the reactivity order ArS- > RS-, ArO- > ROH > RO-, ArSH, ArOH, RSH.

Facile difluoromethylation of aliphatic alcohols with an S-(difluoro-methyl)sulfonium salt: reaction, scope and mechanistic study.

A facile and practical approach for the difluoromethylation of aliphatic alcohols with an S-(difluoromethyl)sulfonium salt was developed. A wide variety of alcohols with broad functional groups are compatible to furnish the corresponding alkyl difluoromethyl ethers in good to excellent yields under mild reaction conditions. Control experiments and DFT computational studies suggest that the difluoromethylation of alcohols mainly proceeds via a difluorocarbene pathway involving a five-membered transition state with the participation of water, whose crucial role in this reaction was also elucidated by control experiments.

Chiral Hydroxytetraphenylene-Catalyzed Asymmetric Conjugate Addition of Boronic Acids to Enones.

( S)-2,15-Br2-DHTP-catalyzed asymmetric conjugate addition of boronic acids to ß-trifluoromethyl α,ß-unsaturated ketones and enones was studied. The reaction afforded the corresponding Michael addition products in moderate to high yields with excellent enantioselectivities (up to 99:1 er). This catalytic system features mild reaction conditions, high efficiency, and tolerance to heteroarylboronic acids.

PtCl2-Catalyzed Cycloisomerization of 1,8-Enynes: Synthesis of Tetrahydropyridine Species.

The cycloisomerization of 1,8-enynes in the presence of platinum(II) chloride was developed to generate bicyclic nitrogen-containing heterocycle species via 6- endo-dig cyclization and [3,3]-sigmatropic rearrangement in acceptable to good yields. The related control experiments and preliminary mechanistic studies indicate a plausible mechanism involving 1,6- endo-dig aminoplatination of the alkyne and allylic [3,3]-sigmatropic rearrangement with total inversion of the allylic moiety.

Stereospecific Iron-Catalyzed Carbon(sp2)-Carbon(sp3) Cross-Coupling with Alkyllithium and Alkenyl Iodides.

An efficient synthetic protocol involving iron-catalyzed cross-coupling reactions between organolithium compounds and alkenyl iodides as key coupling partners was achieved. More than 30 examples were obtained with moderate to good yields and high stereospecificity. Gram-scale and synthetic applications of this procedure are recorded herein to demonstrate its feasibility and potential utilization.

Ligand-Free Iron-Catalyzed Carbon (sp2)-Carbon (sp2) Oxidative Homo-Coupling of Alkenyllithiums.

A new strategy was developed for the efficient synthesis of di-, tetra-, and hexa-substituted 1,3-butadienes. This one-pot procedure involves lithium-iodine exchange to generate the corresponding vinyllithium intermediates. A subsequent iron-catalyzed ligand-free oxidative homo-coupling eventually led to the formation of 1,3-butadienes in acceptable to excellent isolated yields.

Chiral iminophosphorane catalyzed asymmetric sulfenylation of 4-substituted pyrazolones.

An excellent level of enantioselectivity in asymmetric sulfenylation of 4-substituted pyrazolones was achieved with chiral iminophosphorane as the organocatalyst under continuum solvation conditions (up to 99% ee). Importantly, this catalytic process features high efficiency with excellent enantioselectivities, easy separation of products, low catalytic loadings and scale-up to grams without loss of enantioselectivity.

Air- and Light-Stable S-(Difluoromethyl)sulfonium Salts: C-Selective Electrophilic Difluoromethylation of ß-Ketoesters and Malonates.

Air- and light-stable electrophilic difluoromethylating reagents, S-(difluoromethyl)- S-phenyl- S-(2,4,6-trialkoxyphenyl) sulfonium salts were successfully developed, and the introduction of intramolecular hydrogen bonds plays a crucial role for the stabilities and reactivities of these reagents. C-selective difluoromethylation of a broad range of ß-ketoesters and malonates proceeded smoothly under mild reaction conditions to give good to excellent yields with excellent C/O regioselectivities.

Gold(I)-Catalyzed Tandem Cycloisomerization of 1,5-Enyne Ethers by Hydride Transfer.

A novel gold-catalyzed tandem protocol, initiated by hydride transfer in the presence of catalytic (C6 F5 )3 PAuCl/AgSbF6 , for the formation of fused polycyclic ring systems has been achieved. This tandem reaction provides rapid access to various fused polycyclic species in a single chemical operation, leading to stereospecific formation of two carbon-carbon bonds and three rings.