Abstract A new method for CF 3 SO 2 Na‐based direct trifluoromethylthiolation of C(sp )H bonds has been developed. SSCF is generated in situ from cheap and easy‐to‐handle Na, the presence CuCl can be used electrophilic indoles, pyrroles, enamines. The extended to perfluoroalkylthiolation reactions using R f Na.

Axially chiral styrenes are of great interest since they may serve as a class novel ligands in asymmetric synthesis. However, only recently have strategies been developed for their enantioselective preparation. Thus, the development and efficient methodologies is highly desirable. Herein, we reported first tandem iridium catalysis general strategy synthesis axially enabled by Asymmetric Allylic Substitution-Isomerization (AASI) using cinnamyl carbonate analogues electrophiles naphthols...

Lead azide (LA) is a widely utilized primary explosive, serving as the initiating charge in blasting caps or detonators to start detonation process of secondary explosives. The toxicity and environmental concerns associated with LA have led regulatory restrictions increased scrutiny, prompting search for lead-free alternatives. highly sensitive toward heat, shock, friction, which poses safety challenges during manufacturing, handling, storage. Developing lead-free, environmentally friendly,...

A newly developed regio- and stereoselective radical addition of alkyne under metal-free conidtions has been disclosed. This chemistry, in which odorless sodium arenesulfinates place thiols are used as the sulfur reagent, provides an efficient, one-pot approach for generation β-iodoalkenyl sulfides, can be easily further functionalized to derive various alkenes alkynyl sulfides rendering this methodology attractive both synthetic medicinal chemistry.

An operationally simple and selective method for the direct conversion of benzylic C–H to C–F obtain mono- difluoromethylated arenes using Selectfluor™ as a fluorine source is developed.

A 2-fluoro-1,3-dicarbonyl-initiated one-pot Michael addition/[5 + 1] annulation/dehydrofluorinative aromatization reaction sequence is introduced for regioselective synthesis of di-, tri-, tetra-, and pentasubstituted pyridines as well fused pyridines. This simple modular performed using readily available starting materials under transition-metal catalyst-free conditions.

α,α-Difluorodiaroylmethane can be used as a nucleophilic difluoromethylation reagent for generating α-thioaryl-α,α-difluoroacetophenones (Ar1COCF2SAr) and difluoromethylthiolated arenes (ArSCF2H) under transition-metal-free conditions. The reaction selectivity is mainly dependent on temperature. method has also been extended to the synthesis of α-thioaryl-α-monofluoroacetophenones using α-monofluorodibenzoylmethane. Moreover, benzoyl cation derived from α,α-difluorodibenzoylmethane react...

Abstract A simple and practical method of fluoroalkylthiolation using fluoroalkylsulfonyl chlorides (R f SO 2 Cl, R =CF 3 , C 4 F 9 8 17 CF H CH ) has been developed. These easy‐to‐handle reagents are powerful can be used for electrophilic electron‐rich arenes thiols diethyl phosphite as reducing agent. magnified image

Abstract Regioselective arylthiolations of aromatic amines, arenols and ketones via C–H bond functionalization have been achieved with I 2 PPh 3 in an aqueous system, whereby arylsulfenyl radicals are situ generated from odorless sodium arylsulfinates. The can react free anilines containing electron‐withdrawing groups complex substrates (estrone progesterone). Further experiments quantum chemical calculations were also performed to deduce a mechanism for the formation radicals. magnified image

A newly developed aqueous system with acid and phosphide was introduced in which odorless stable sodium arylsulfinates can situ generate arylsulfenyl radicals. These radicals have high reactivity to react alkynes, alkenes, H-phosphine oxides for the synthesis of alkyl alkenyl sulfides phosphonothioates. The control experiments quantum calculations are also performed gain insights into generation mechanism Notably, chemistry is free thiol odors, organic solvents, metals.

Axially chiral molecules bearing multiple stereogenic axes are of great importance in the field organic chemistry. However, efficient construction atropisomers featuring two different types has rarely been explored. Herein, we report novel atroposelective synthesis configurationally stable axially B,N-heterocycles. By using stepwise asymmetric allylic substitution-isomerization (AASI) strategy, diaxially B,N-heterocycles B-C and C-N that related to moieties enamines arylborons were also...

The preparation of FSG-supported palladium nanoparticles and their application in direct C-2 arylation indoles are presented. Moderate to good yields were obtained with ultra-low catalyst loading. could be easily recovered by simple workup reused up seven runs only a slight decrease its activity.

Abstract A method for direct difluoromethylthiolation of Ar−H bonds is introduced. The stable and easy‐to‐handle HCF 2 SO Na reduced with (EtO) P(O)H in the presence TMSCl to generate S + regioselective aromatic compounds including indoles, pyrroles, activated benzenes. This also applicable trifluoromethylthiolation CF 3 perfluoroalkylthiolation R f arenes heteroarenes. Reaction mechanisms associated metal‐free electrophilic fluoroalkylthiolation reactions are discussed. magnified image

The unprecedented use of CF3SO2Cl for direct bifunctional chloro-trifluoromethylthiolation alkenes and alkynes is reported. CF3SCl, which generated by the reduction PPh3, undergoes electrophilic addition then chlorination to give bifunctionalized products without using an additional chlorine source. method also applicable chloro-difluoromethylthiolation CF2HSO2Cl.

Trifluoromethanesulfinyl chloride (CF3 SOCl) has been introduced as a new reagent for C-H trifluoromethylthiolation of indoles, thiophenes, and ketones under catalyst-free conditions in the absence reductant. The disproportionation CF3 SOCl to SO2 Cl SCl provides two pathways trifluoromethylthiolation. Direct with or trifluoromethylsulfoxidation is followed by reduction SOCl. This can be used functionalize benzothiophenes, benzofurans, indenes promotion Ag2 CO3 . It also thiols...

A new strategy for the synthesis of 3,5-disubstituted phenols is established through one-pot Robinson annulation α,β-unsaturated ketones with α-fluoro-β-ketoesters followed by in situ dehydrofluorination and tautomerization. This method has been extended to polysubstituted applied preparation biologically active compounds.

A newly developed CF3SO2Na-based trifluoromethylation of secondary amines has been disclosed, and the method successfully extended to configuration perfluoroalkyl using RfSO2Na, complementing established synthesis strategy trifluoromethyl amines. Advantages include good functional group tolerance, mild conditions, inexpensive or easy-to-handle materials. Mechanistic probes indicate that thiocarbonyl fluoride formed in situ is key intermediate reaction.

Abstract Axially chiral N ‐substituted quinazolinones are important bioactive molecules, which presented in many synthetic drugs. However, most strategies toward their atroposelective synthesis mainly limited to the axially arylquinazolinone frameworks. The development of modular methods access diverse quinazolinone‐based atropisomers remains scarce and challenging. Herein, we report regio‐ ‐vinylquinazolinones via strategy asymmetric allylic substitution‐isomerization. catalysis system...

Abstract Additive manufacturing (AM) of copper through laser‐based processes poses challenges, primarily attributed to the high thermal conductivity and low laser absorptivity powder or wire as feedstock. Although use salts in vat photopolymerization‐based AM techniques has garnered recent attention, achieving micro‐architected with density remained elusive. In this study, we present a facile efficient process create complex 3D structures superior electrical hardness. The entails formulation...

Abstract A novel and efficient domino process has been developed for the synthesis of 1,4‐benzoxazepine derivatives from a range readily accessible N ‐tosylaziridines, 2‐iodophenols isocyanides. This involves aziridine ring‐opening reaction with 2‐iodophenol, followed by palladium‐catalyzed isocyanide‐insertion reaction. regioselective high‐yielding transformation could be extended to its application natural products biologically interesting heterocycles. magnified image