Transition metals have been an indispensable component of modern catalysis and among these palladium is the top‐ranked choice of chemists as catalyst. After the several important developments of palladium catalysed C‐C cross‐coupling reactions, carbonylative transformations have been realised as an attractive post modification of these reactions. Carbonylative Suzuki‐Miyaura coupling reaction is among

The utilization of carbon dioxide as a building block in organic synthesis has become a highly sought‐after research area. In this minireview, an overview of recent advances on carboxylations using carbon dioxide via visible light photoredox and transition‐metal dual catalysis is given. The merging of these methods provides new avenues to construct carboxylates.

An order‐of‐magnitude improvement in the production of phenylacetaldehyde to 3.37 M (405 g L‐1) from the enzymatic isomerisation of styrene oxide was achieved. A small ubiquitin‐related modifier (SUMO) tag increases the productivity of the whole‐cell biocatalytic system by enhancing the expression of active membrane‐bound styrene oxide isomerase (SOI) while retaining enzyme catalytic efficiency and

A Rh(III)‐catalyzed Csp2‐Csp3 bond cleavage/carbonylethylation of α‐indolyl alcohols with allylic alcohols has been reported. This transformation involved a cascade C‐C bond cleavage/C‐C bond formation, and provides a novel approach to assemble 2‐carbonylethylindole skeletons.

In the past decades, there has been a dramatic increase in the developments of novel methods for the activation/functionalization of inert C–H bonds as these protocols are not only competent, reduce the waste materials in addition to the reaction time and multiple steps but also allows the reaction to be carried out in a highly regio‐specific manner under operationally simple yet effective reaction

Herein, we describe a practical protocol for efficient, mild, visible‐light‐induced three‐component intermolecular trifluoromethyl‐alkenylation reactions of unactivated alkenes. The protocol has good functional group tolerance and a broad substrate scope. Using this protocol, we not only introduced a trifluoromethyl group into alkenes but also converted unactivated alkenes to styrene‐based activated

The preparation of oxazolidinones by the hypervalent iodine mediated cyclization of allylcarbamates is described. A versatile range of substrates can be converted into substituted oxazolidinones primed for further transformations. Derivatization of the products at both ends is demonstrated. A preliminary attempt at the enantioselective formation of an oxazolidinone using a chiral iodane is also presented

Regioselective cobalt‐catalyzed [2+2+2] cycloaddition using fluorine‐containing diynes with nitriles was described. Cycloaddition of fluorinated diynes with nitriles under the influence of CoCl2(phen), zinc bromide, and zinc dust in dichloroethane at 80 °C for 3 h took place smoothly, exclusively affording the corresponding α‐fluoroalkylated pyridines in excellent yields. In addition, dinitriles as

Abstract. A clean method has been developed for the α‐allylation of phenyl and alpha alkyl phenyl acetonitrile with allylic alcohols. The reaction is catalyzed by nickel complexes in situ generated from a combination of Ni(cod)2 and the dppf ligand and performed at 80°C in methanol as reaction solvent. Accordingly to this simple and base‐free protocol that only yields water as a side‐product, many

In recent years, great improvements have been made on palladium‐catalyzed radical reactions. Emerging elegant methodologies of radical involved palladium‐catalyzed transformations provide more and more effective strategies for the construction of complex heterocyclic compounds and applications in drug discovery. It is universally known that Pd(0)/(II)/(IV)‐mediated reactions usually undergo two‐electron

A simple and efficient visible‐light‐promoted selenylation/cyclization of enaminones have been realized for the practical synthesis of 3‐selanyl‐4H‐chromen‐4‐ones. This reaction is performed in the mild conditions, no transition metal catalyst or photocatalysts and no additional oxidants are required. In addition, the 3‐selanyl‐4H‐chromen‐4‐ones could be easily converted to selanyl‐functionalized pyrimidines

Silver complexes with 5‐(4‐(tert‐butyl)‐1(H‐imidazol‐1‐yl)‐imidazo[1,5‐a]pyridin‐3‐ylidene ligands were synthesized as metal‐imidazole acid‐base cooperative catalysts. Single crystal XRD analysis revealed that the silver atom was located in the vicinity of the imidazole ring and that cationic silver complexes formed dimers through coordination between the silver metal and the imidazole pendant. These

In this review, the pivotal achievements and recent advances in catalytic asymmetric aza‐DAR reported up to 2020 are retrospectively considered and their potency for enantioselective synthesis of useful chiral piperidine, quinoline, pyridazine, oxazine and oxadiazine derivatives and fused compounds of higher molecular complexity bearing these pharmacology‐relevant heterocyclic scaffolds is demonstrated

Mechanochemical reactions by milling, grinding or other types of mechanical action have emerged as a salient green approach because of its wide applications towards academic and industrial chemical communities in sustainable solvent‐free/solvent‐less processes. Liquid‐assisted grinding (LAG) as an extension of traditional solvent‐free mechanochemical techniques by which a small amount of liquid is

The C‐H functionalization of benzo‐fused cycloalkanones represents a synthetic challenge since such scaffolds display different activation sites, at sp2 and sp3 carbons, a bicyclic structure and various sizes of the cycloalkanone ring. Anticipating the outcome of C‐H functionalisation and the impact of the presence and size of the cycloalkanone ring would help to foresee synthetic routes to more complex

A selective palladium‐catalyzed C(sp) arylation/carbocyclization/iodonium migration reaction sequence has been accomplished. Novel 2‐iodo‐1‐aryl‐9H‐carbazoles are now easily available. As this result is contrary to the selectivity observed using gold catalysis, the formation of 2‐iodo‐carbazoles is noticeable, suggesting a metal‐controlled cyclization through chemo‐ and regioselective 1,2‐alkyl migration

Phenanthridine derivatives are one of the most intensively studied families of biologically active compounds. There has been considerable scientific interest in the turn of this century in the synthesis of these N‐containing heterocycles as they are prevalent in many alkaloids and also possess striking biological activities including antibacterial, antifungal, antitumor activities. In this regard,

Chiral 2‐alkylquinazolinones are key synthetic intermediates, but their preparation in high optical purity is challenging. Thus, a multicomponent procedure integrating anthranilic acids, N‐Boc‐amino acids, and amines in the presence of methanesulfonyl chloride, N‐methylimidazole, and copper(II) chloride was developed to mildly afford N‐Boc‐2‐alkylaminoquinazolin‐4(3H)‐ones with excellent preservation

To develop highly efficient synthetic reactions is quite important in organic chemistry. Cross dehydrogenative couplings (CDC) utilize C‐H bonds of substrates to construct new C‐X (X=C, S, O, N, P) bonds. For CDC, the pre‐functionalization of reaction substrates can be avoided and the C‐X (X=C, S, O, N, P) bonds can be newly formed by simple and efficient synthesis routes. Meanwhile, water is increasingly

A palladium‐catalyzed carbonylative reaction of trifluoroacetimidoyl chlorides and nitro compounds for the construction of pharmaceutically valuable 2‐(trifluoromethyl)quinazolin‐4(3H)‐ones has been achieved. In this transformation, Mo(CO)6 is regarded as both a convenient CO source and a reducing reagent. This newly developed protocol can be compatible with various kinds of nitro compounds and be

The particular nature of boron compounds allows an ample modularity of their properties ranging from Lewis acids, C‐nucleophiles, B‐nucleophiles or even conjunctive reagents for new synthetic manipulations. Moreover, the increasing demand for functionalized boron derivatives for pharmaceutical or material science applications requires the development of new synthetic methods for boron introduction

A catalyst and additive‐free strategy for selective ring‐opening selenocyanation of saturated heterocycles with elemental selenium and TMSCN is developed, affording a series of aliphatic selenocyanates and selenaheterocycles. In the case of unprotected unstrained N‐heterocycles, the reactions offer ammonium selenonitriles that prove to be an efficient selenonitrile reagent.

The Rh(III)‐catalysed C‐H couplings of 1‐naphthols with gem‐difluoromethylene alkynes have been realized for the direct construction of difluorinated dihydrobenzo[de]chromenes with broad substrate/functional group compatibility and good regio‐/chemoselectivity and in an atom‐economic manner. The unique fluorine effects account for the unconventional reaction path involving intramolecular 1,3‐hydrogen

Herein, a three‐component reaction of benzimidazoles, nitroalkenes and elemental sulfur has been developed. Cheap and easily available salicylic acid found to be an efficient mediator for the present transformation. This protocol provides facile access to structurally significant imidazo[2,1‐b]thiazole skeleton from simple raw materials, with a range of compatible synthetically useful functionalities

Herein, a base‐controlled protocol was developed for the C‐N coupling of primary amines and 2‐chlorobenzimidazoles, affording a handful of secondary or tertiary amines in a selective fashion. Moreover, this protocol was realized under transition‐metal‐free conditions, and the variation of the base from iPr2NH to LiOtBu completely switched the selectivity from monoarylation to diarylation. Further investigations