The Mizoroki‐Heck(M‐H) reaction is one of the most valuable reactions for functionalizin C‐C double bonds in the presence of a Pd catalyst. This protocol is suitable for the reaction of a C(sp 2 )‐halide with a terminal olefin to produce a trans‐1,2‐disubstituted olefin. However, reports of the M‐H reaction of internal olefins are rare and impractical due to low reactivity of internal olefin and problem of product diastereoselectivity. In this review, we summarise M‐H reactions of internal olefins with aryl‐ or alkyl halides.

Phenyl‐pyrazinyl‐2‐pyridyl‐2‐pyrimidinylmethane (1) has been synthesized in four steps from 2‐(chloromethyl)pyridine. This compound is chiral and expected to show the metal coordinating ability because three of four aryl groups have the nitrogen atom at ortho‐position with respect to the central carbon atom. The X‐ray crystallographic analysis of rac‐1 unambiguously revealed the tetraarylmethane framework, but the nitrogen atoms could not be assigned. The optical resolution of 1 was achieved by chiral HPLC. Besides the CD spectra of the two fractions exhibited opposite signs as expected, the solvent effect of the CD spectra was also observed. According to the calculated CD curve based on time‐dependent density functional theory (TDDFT) method, the first eluted fraction is the R isomer in terms of absolute configuration. It should be noted that the CD spectrum of 1 was also changed by the addition of the transition metal ions because of the formation of the metal complexes of 1. The Job plot and the electrospray ionization (ESI) mass spectrum of the solution of rac‐1 in the presence of Cu2+ ion revealed that the stoichiometry of 1 and Cu2+ was 2:1.

Described herein is that an indium(III) compound effectively catalyzes a reductive insertion into either diaryl or dialkyl disulfides with orthoesters to produce a variety of dithioacetal derivatives. This method could also be adapted to the diselenoacetalization of diselenides. During a series of reductive insertions using this method, it is noteworthy that an orthoester functions as a novel masked methylene moiety.

A simple and efficient Pd(II)‐catalyzed site‐selective direct arylation strategy was demonstrated for the synthesis of 8‐arylquinoline‐ N ‐oxide derivatives using quinoline‐ N ‐oxides and (aryl)(mesityl)iodonium triflates. A series of control experiments were carried out to elucidate the reaction mechanism. The synthetic potential was extended with the C‐2 post‐modification of the final derivative.

Herein, we report the reaction of quinoline with diphenylphosphine oxide in the presence of visible light without catalyst. The reaction completes in 24 h under the mild conditions and the substrates are well tolerant. This method provides a straightforward and environmentally friendly access to diphosphorousylated quinoline compounds. Similarly, this method can also enlighten the phosphating of some heterocyclic compounds.

We developed a cationic iron(III) salt initiator for radical cation‐induced [4 + 2] cycloaddition. Fe(OTf)3 [or Fe(ClO4)3] behaves as a highly active oxidant for both electron‐deficient and electron‐rich dienophiles. The scope of substrates is much broader than with FeCl3 reported previously. With highly active Fe(OTf)3, we demonstrate a formal total synthesis of Heitziamide A.

We have developed a versatile synthetic method for the construction of spirocyclic guanidines in moderate yields by intramolecular dearomative oxidative cyclization of guanidino phenols using the hypervalent iodine reagent 4‐chloro‐1‐(diacetoxyiodo)benzene in 2,2,3,3‐tetrafluoro‐1‐propanol.

A N‐heterocyclic carbene‐catalyzed activation of ynals for the rapid assemble of pyridine derivatives with important utilities was reported. This successful strategy using NHC‐bounded alkynyl acyl azolium as the key intermediate, and further improved the application of N ‐Ts 2‐aminoacrylate as a nucleophile. Importantly, this work introduces an ester substituent to pyridines which could easily transformed to other functional groups.

We synthesized a bidentate bispyridylhydrazone functionalized copillar[5]arene ( BACP5A ) which can self‐assemble via strong intermolecular hydrogen bonds. BACP5A self‐assembled into size‐controllable vesicles, with the synergistic interactions of intermolecular hydrogen bonding and internal amphiphilicity, which are responsive to pH, temperature and solvent. BACP5A was used to form a bidentate metal‐ligand coordinated complex with Zinc trifluoromethanesulfonate in which a new rectangular cavity containing hexacoordinated zinc ions occurred between two adjacent BACP5A . This type of coordinated complex may be employed for the development of new macrocyclic‐based artificial enzymes.

An efficient rhodium(III)‐catalyzed C‐H bond naphthylation reaction is described for the synthesis of diverse anilides and benzamides bearing naphthyl substituents. The substrate scope is broad. The products could be facilely elaborated to various synthetically useful intermediates. To the best of our knowledge, using 7‐azabenzonorbornadienes to achieve naphthylation via transition‐metal‐catalyzed C−H activation has not been reported before.

Herein we report a comparative study of nickel‐catalyzed synthesis of pyrimidines via dehydrogenative multi‐component coupling of alcohols and amidines using two different class of nickel catalysts ( 1a/1b and 2a/2b ) differing with respect to their mode of action during catalysis. The catalysts 1a and 1b are two tetracoordinate Ni(II)‐complexes containing two apparently redox‐inactive tetraaza macrocyclic ligands while the catalysts 2a and 2b are square planar Ni(II)‐complexes featuring redox‐active diiminosemiquinonato type scaffolds. Catalyst 1a and 1b dehydrogenate alcohols via two‐electron hydride transfer pathway involving energetically demanding nickel‐centered redox events while in the presence of 2a and 2b dehydrogenation of alcohols proceeds via one‐electron hydrogen atom transfer (HAT) pathway via synergistic participation of metal and ligand centered redox processes avoiding high energy nickel centered redox events. Detailed substrate screening and a few control experiments were performed to unveil the reaction sequence and understand the advantages/disadvantages of these two pathways.

A new type of optically pure secondary‐amino aromatic Tf‐amide organocatalysts can be easily prepared from commercially available L ‐hydroxyproline. The chemical behavior of these organocatalysts was investigated by the application to asymmetric aldol reactions. Among these, catalyst 2a efficiently catalyzed direct asymmetric aldol reactions of cycloalkanones and substituted benzaldehydes, which afforded the corresponding aldol adducts in good yield with good to excellent anti‐ and enantioselectivity.

1,1‐Difluoroethylated aromatic compounds are of increasing importance in agrochemicals and pharmaceuticals. The direct introduction of difluoroethyl (CF 2 CH 3 ) group(s) onto aromatic rings using CH 3 CF 2 Cl, a cheap and available raw material, still remains a great challenge because of the relatively inert C‐Cl bond of CH 3 CF 2 Cl. Herein, we disclose a nickel‐catalyzed 1,1‐difluoroethylation of (hetero)aryl halides with CH 3 CF 2 Cl. The reaction exhibits good functional group tolerance and is regarded as a practical method for synthesis of (1,1‐difluoroethyl)arenes.

We report here a highly efficient method for direct alkynylations of 3‐alkyl/aryl/indolyl 2‐oxindoles using a series of 5‐(alkynyl)dibenzothiophenium triflates (3a‐e) under transition‐metal free condition. This direct electrophilic alkynylation method give access to a variety of 2‐oxindoles having quaternary center at the benzylic position in an operationally simple and inexpensive procedure. Further, chemoselective alkynylations could be realized in case of N‐H free 2‐oxindoles and 3‐(indolyl) 2‐oxindoles to afford a number of 3,3‐disubstituted 2‐oxindoles. The methodology is eventually employed in the total synthesis of (±)‐deoxyeseroline (1a) as well as C(3a)‐indolyl furoindoline moiety (31).

The omnipresent character of C‐H bonds in organic molecules gives a wide variety of opportunities for the synthesis of a number of functionalized molecules by the activation of the C‐H bonds. One of those methods is the gold catalyzed C‐H activation. Recent developments in the area of gold catalyzed C‐H activation involves the annulation reactions leading to the formation of heterocyclic compounds via gold catalyzed C‐H activation, Au‐catalyzed cross coupling reactions, C‐H functionalization reactions with high atom efficiency and C‐H activation involving organic transformations. In this short review we summarize the developments and studies carried out in gold catalyzed C‐H activation in the past decade.

Porphyrinoids in which one or two pyrrole rings are replaced with polycyclic aromatic hydrocarbons/heterocycles such as naphthalene, phenanthrene, biphenyl, bipyridine, phenanthroline, etc. are a new class of porphyrinoids represented as polycyclic aromatic hydrocarbons/heterocycles (PAHs) embedded porphyrinoids. These macrocycles possess the structural features of both polycyclic aromatic hydrocarbons/heterocycles and cyclic polypyrrolic porphyrinoids. The PAHs embedded porphyrinoids have drawn significant interest in recent times because of the following: (1) these macrocycles exhibit different π‐conjugation pathways unlike porphyrinoids which exhibit circular conjugation pathways in their macrocyclic rings with various molecular structures; (2) the PAHs embedded macrocycles show variable degree of aromaticity which varies from weak aromaticity to antiaromaticity and (3) the PAHs embedded porphyrinoids provide unique ligand environment to form stable coordination and organometallic complexes in which metals may show uncommon oxidation states and unusual reactivity. All these above‐listed features depend on polycyclic aromatic hydrocarbon/heterocycle moiety present as a part of porphyrinoid macrocyclic framework. This mini‐review focuses on the synthesis of different polycyclic aromatic hydrocarbons/heterocycles embedded porphyrins, contracted porphyrins and expanded porphyrins and briefly discusses their structural, spectral, aromatic and coordination properties.

Alkynes are useful synthetic building blocks that occur in many naturally occurring molecules and have the potential to be easily modified for further natural products and drug synthesis applications. Given the versatility of the alkyne functionality, various synthetic methods (most palladium‐based) are known in literature allowing the installation to take place under different reaction conditions. A single catalytic system (without Pd) however, if developed could provide a single point solution for the installation of the alkyne moiety and keeping this in mind, we report herein a highly active palladium‐free Cu/carbazole‐based NHC catalyst system allowing homocoupling and heterocoupling of alkynes at ambient temperature. Using a combination of Cu/NHC‐catalyzed homocoupling/deprotection/heterocoupling sequence tetraynes have also been synthesized in good yields. The Cu/NHC catalyst system was also able to catalyze a palladium‐free Sonogashira reaction of synthetically useful nucleosides, which is the first to be reported in literature. Finally, an example of a one‐pot Sonogashira reaction/cyclisation sequence for the synthesis of indoles from 2‐iodoaniline has also allows portrayal of the full‐range of activity of the developed system.

This work provides the first example of water mediated decomposition of N ‐sulfonylhydrazones in the absence of any base or catalyst to use as a sulfonyl‐transferring reagent in the selective sulfa‐Michael reaction. A wide range of substituted N ‐sulfonylhydrazones were tested as a source of sulfonyl anion with enones or acrylonitrile which in turn provided the γ‐ keto/nitrile sulfones in very good yields. Additionally, we have performed a rigorous computational mechanistic study to investigate the role of water which demonstrates the key role of water in the hydrogen abstraction from N‐tosylhydrazone to initiate the reaction.

The development of chiral selenium catalysts for asymmetric transformations has become a pre‐eminent topic in the field of organocatalytic chemistry. Herein, we report the development of chiral bifunctional selenide catalysts bearing a hydroxy group and discuss their application to asymmetric bromolactonization reactions. The importance of the bifunctional design of chiral selenide catalysts for enantioselective bromolactonizations was clearly demonstrated in the present work.