It's all in the solvent: An enantioselective variant of an aza-Wacker-type cyclization that gives isoindolinones containing tetrasubstituted carbon centers α to the nitrogen atom has been developed (see scheme; tfa=trifluoroacetate). The use of a highly coordinating solvent is crucial for the activity of the catalyst and the stereoselectivity the reaction (up to 99 % ee).

A method was developed for the nickel-catalyzed phosphonylation of aryl mesylates and tosylates with H(O)PR(1)R(2). To the best of our knowledge, this is the first example of nickel-catalyzed C-P coupling of aryl mesylates and tosylates. Most of the substrates gave moderate to good yields under our catalytic system.

The achievements on palladium-catalyzed carbonylative multicomponent reactions (CMCR) have been summarized and discussed according to the type of carbonylation reaction involved.

Multicomponent reactions, especially those involving four or even more reagents, have been a long-standing challenge because of the issues associated with balancing reactivity, selectivity, and compatibility. Herein, we demonstrate how the use of a reagent capsule provides straightforward access to synthetically valuable thiochromenone derivatives by a palladium-catalyzed carbonylative four-component reaction. To the best of our knowledge, this is the first example of applying a capsule to prevent catalyst poisoning and undesired side reactions of the multicomponent reaction.

Polyoxometalates (POMs) are a diverse class of anionic metal-oxo clusters with intriguing chemical and physical properties. Owing to unrivaled versatility and structural variation, POMs have been extensively utilized for catalysis for a plethora of reactions. In this focused review, the applications of POMs as promising catalysts or co-catalysts for CO2 conversion, including CO2 photo/electro reduction and CO2 as a carbonyl source for the carbonylation process are summarized. A brief perspective on the potentiality in this field is proposed.

The palladium-catalyzed chemoselective carbonylation of bromoaryl triflates is reported. The selective C-Br bond versus C-OTf (OTf=triflate) bond functionalization can be remarkably tuned by the combination of the ligand [4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) vs. 1,1'-bis(diphenylphosphino)ferrocene (DPPF)] and the solvent (toluene vs. DMSO). The respective ligand and solvent effects are rationalized by DFT calculations. In contrast, the monodentate ligands BuPAd and tBu P prefer the selective C-Br bond activation and are solvent insensitive.

The structural diversity and tenability observed in POMs has encouraged extensive investigations into their catalytic activity. Based on the structural classification of POMs, this review summarizes recent advances relating to POM‐catalyzed selective oxidation and places most emphasis on dynamic developments from 2015 onwards. Work which contributes to comparing the catalytic performance of POMs with delicate structural differences (e.g. the same type of POM structure with differences of the heteroatom, addenda, protonated state or counter‐ion) and in elucidating the origin/distinction of catalytic activity, as well as reasonable mechanisms, are especially highlighted.

An unexpected palladium-catalyzed carbonylatives ynthesis of 2,3-disubstituted chromones has been developed. Startingf rom 2-bromofluorobenzenesa nd ketones,t he corresponding chromones were produced in good yields. By control experiments,this transformation was found to proceed through as equential carbonylation/Claisen-Hasse rearrangement/intramolecular nucleophilic aromatic substitution approach (S N Ar). More specifically,t he reaction sequence started with ap alladium-catalyzed carbonylation of the ketone with o-bromofluorobenzene to give the vinyl benzoates,w hich subsequently transformed into 1,3-diketones via aC laisen-Hasse rearrangement. Thef inal products were produced after an intramolecular S N Ar reaction of the in situ formed 1,3-diketone. Scheme 1. Pathways to 2,3-disubstituted chromones.Scheme 2. Thechemoselectivity on carbonylation of the deoxybenzoin substrate.