Abstract The copper‐catalyzed stereoselective defluorinative borylation and silylation of gem ‐difluoroalkenes was developed. protocol led to the exclusive formation Z type monofluoroalkenyl borons silanes in generally good efficiency with broad substrate scope. products formed could be readily transformed other F‐containing molecules by taking advantage versatile reactivities C−B C−Si bonds. Experimental theoretical mechanistic studies were conducted which support an olefin insertion/ syn...

A facile oxidative radical cyclization of aryl alkynoate esters for the synthesis 3-trifluoromethylthiolated and 3-thiocyanated coumarins is developed.

Abstract Recent years have witnessed a renaissance of radical cross‐coupling cycloketone oximes which served as active cyanoalkyl via ring fragmentation in various transformations. It provided an efficient and practical strategy to introduce groups into organic compounds without using toxic cyanide sources. In this review, comprehensive overview recent advances the field redox‐active oximes‐based cross‐couplings were covered. This review was categorized two broad parts: non‐photocatalyzed...

The pyrrole moiety is an important structural motif in functional materials, natural products, and pharmaceuticals. More more synthetic strategies toward pyrroles have emerged, where various efficient building blocks are developed these synthons enable the syntheses of with different numbers components. However, no review specifically summarizes according to type number employed blocks. To aid researchers design appropriate substrates for synthesis, herein we summarized advances classified...

Transition-metal-catalyzed alkylation of (hetero)arenes with three-membered carbo-/heterocycles involving C–H activation and ring scission has been greatly developed over the past few years. The chelation-assisted strategies for controlling reactivity site selectivity in these protocols include use nitrogen-containing directing groups, pre-existing functional a Catellani-type intermediate, thereby providing rapid access to numerous oxygen- or heterocyclic systems. This review gives an update...

Two categories of tetrasubstituted phenols were prepared via the cycloaddition reaction vinyl sulfoxonnium ylides with cyclopropenones in a switchable manner. Copper carbenoid was proposed as active intermediate process 2,3,4,5-tetrasubstituted formation, while 2,3,5,6-tetrasubstituted generated direct [3 + 3] annulation under metal-free conditions. Further synthetic applications also demonstrated.

A rhodium(III)-catalyzed C-H direct allylation reaction with 4-vinyl-1,3-dioxolan-2-ones has been developed. The provides a facile and stereoselective access to substituted-(E)-allylic alcohols under mild redox-neutral conditions. Olefinic activation is applicable, giving multifunctionalized skipped dienes in good yields. Minimal double-bond migration was observed.

The synthesis of halogenated and trifluoromethylated α-boryl ketones via a one-pot oxidative difunctionalization alkenyl MIDA boronates is reported. These novel densely functionalized organoborons bearing synthetically functionally valuable carbonyl, halogen/CF3 boronate moieties within the same molecule are challenging for chemist, but have great synthetic potential, as demonstrated by their applications in straightforward borylated furans. generality this reaction was extensively...

Abstract The amino group is one of the most prevalent functional groups present in a wide range organic molecules, which has been widely applied various synthesis and pharmaceuticals. Alkyl amines could be converted single step into Katritzky salts serve as alkyl radical precursors to construct C−C bonds C−X via C(sp 3 )−N cleavage. This deaminative functionalization carried out under transition‐metal catalysis, photocatalysis, carbene catalysis or promoted by base. In this paper, recent...

A simple and efficient method for the synthesis of diaryl 1,2-diketones has been developed. The reaction represents first example that are synthesized directly from arylboronic acids arylpropiolic by a radical pathway in moderate to good yields. This proceeds under mild conditions with tolerance variety functional groups. Preliminary mechanistic studies were conducted.

Abstract The ring‐opening reactions of N ‐methyliminodiacetyl (MIDA) α‐chloroepoxyboronates with different nucleophiles allow the modular synthesis a diverse array organoboronates. These include seven types α‐functionalized acylboronates and borylated heteroarenes, some which are difficult‐to‐access products using alternative methods. common synthons, α‐chloroepoxyboronates, could be viably synthesized by two‐step procedure from corresponding alkenyl MIDA boronates. Mild reaction conditions,...

Abstract A photoredox‐catalyzed three‐component sulfonaminoformyloxylation reaction between alkenes, N ‐aminopyridinium salts and DMF has been developed, which avoids the usage of erosive formic acid as formyloxylation reagent. Besides DMF, alkyl aryl carboxylic acids proved to be feasible nucleophiles afford various β ‐amino esters. The robustness this method was further demonstrated by its applicability in late‐stage modification biological molecules. Control experiments suggested that a...

Unsymmetrical vicinal diamines have been achieved via the photoredox-catalyzed difunctionalization of alkenes by using N -aminopyridinium salts and nitriles as amination reagents, respectively.

Abstract A silver‐catalyzed oxidative decarboxylative coupling reaction of arylpropiolic acids with H ‐phosphine oxides by using air as the terminal oxidant was developed. The proceeds smoothly under mild conditions to give β‐oxophosphine in moderate good yields. Preliminary mechanistic studies were conducted.

A rhodium(III)-catalyzed C-H allylation of (hetero)arenes by using 2-methylidenetrimethylene carbonate as an efficient allylic source has been developed for the first time. Five different directing groups including oxime, N-nitroso, purine, pyridine, and pyrimidine were compatible, delivering various branched allylarenes bearing hydroxyl group in moderate to excellent yields.

We report a photoredox-catalyzed three-component sulfonaminoalkynylation of alkenes with N-aminopyridine salts and potassium alkynyltrifluoroborate salts. This aminoalkylation reaction underwent radial/polar crossover mechanism, which was distinguished from the previous reports. A variety β-alkynylated sulfonamides were obtained in moderate to excellent yields. The versatility this method further evidenced by its successful application modifying biological molecules advanced stages development.

Recent years have witnessed a rapid growth in the C‐F bond functionalization of trifluoromethylarenes and trifluoromethyl carbonyl compounds, which was promoted by development photoredox catalysis. In this review, photocatalyzed activation compounds via difluoromethyl radical intermediate has been covered. This review categorized into three parts based on modes bond. Several representative instances, conjunction with reaction mechanism, were also deliberated upon.

Abstract 1, 2‐amino alcohols and allyl ether are important motifs present in various biological molecules. Herein, we reported a photocatalyzed decarboxylative cross‐coupling reaction between N ‐arylglycine o ‐allyloxy arylaldehyde, which can integrate the above two one molecule. This protocol featured excellent chemo‐selectivity, mild conditions ready to be scaled up. A potential mechanism was proposed.

An indazolone-directed chemoselective synthesis of 8 H -indazolo [1,2- a ]cinnolines has been realized via cascade Cp*Ir( iii )- and Cp*Rh( )-catalyzed C–H activation/cyclization reaction 1-arylindazolones with sulfoxonium ylides.

Abstract A photo‐induced metal‐free radical hydroboration of various styrenes with NHC‐borane has been developed, which can provide mono‐ and di‐alkylated boranes in a selective manner. Besides, this strategy also be applied to prepare di‐functionalized two different alkyl groups. Mild reaction conditions good functional groups compatibility were observed. Preliminary mechanism for was proposed.

Abstract The synthesis of halogenated and trifluoromethylated α‐boryl ketones via a one‐pot oxidative difunctionalization alkenyl MIDA boronates is reported. These novel densely functionalized organoborons bearing synthetically functionally valuable carbonyl, halogen/CF 3 boronate moieties within the same molecule are challenging for chemist, but have great synthetic potential, as demonstrated by their applications in straightforward borylated furans. generality this reaction was extensively...

Abstract The individual molecules of α‐chloroalkenyl boronates include both an electrophilic C−Cl bond and a nucleophilic C−B bond, which makes them intriguing organic synthons. Reported herein is stereodivergent synthesis E Z N ‐methyliminodiacetyl (MIDA) through the direct chlorination alkenyl MIDA using t BuOCl PhSeCl reagents, respectively. Both reaction processes are stereospecific use sp 3 ‐B boronate key contributor to reactivity. synthetic value products was also demonstrated.

The metal-free reductive N-trifluoroethylation and N-trifluoroacetylation of indoles have been developed. Bench stable inexpensive trimethylamine borane trifluoroacetic acid (TFA) were utilized as the fluorinating reagents, respectively. These transformations switchable on basis altering loading TFA. Preliminary experiments indicated indoline was common intermediate in these two transformations.

The attachment of N-methyliminodiacetyl boron (MIDA boron) to alkenes leads a new type activated alkenes. Synthetic manipulation the alkene double bond while retaining moiety offers an unprecedented opportunity for construction organoborons. These reactions feature unique reactivity, good regioselectivity, and they can be used access organoborons that are historically difficult prepare. Herein, we give brief summary advances in use alkenyl MIDA boronates as starting materials organoboron...

The synthesis of α-boryl halohydrins via difunctionalization alkenyl MIDA boronates has been reported. Intriguing stereoselectivity was found with different halogen sources, which arises from the special stabilizing effect B(MIDA) moiety. transformation provided cis addition products using Cl+ or Br+ as source, while trans were obtained when I+ employed.