Chemistry of Heterocyclic Compounds, Год журнала: 2024, Номер 60(5-6), С. 299 - 303
Опубликована: Июнь 1, 2024
Язык: Английский
ACS Catalysis, Год журнала: 2023, Номер 13(21), С. 14112 - 14120
Опубликована: Окт. 19, 2023
A photocatalytic approach for the C(sp3)–H trifluoromethylthiolation of amides under mild reaction conditions is reported. We have developed a protocol that tolerates large range functional groups and allows functionalization aromatic aliphatic in high yields (26 examples, up to 83% yield) by using low catalytic loading an organophotocatalyst. With this approach, synthesis original fluorinated acyclic thioaminals successfully achieved. Detailed mechanistic studies are conducted enable deciphering oxidative quenching cycle via proton-coupled electron transfer (PCET), allowing formation primary radical at α-position nitrogen.
Язык: Английский
Процитировано
16
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(30)
Опубликована: Май 7, 2024
Abstract Site‐selective ortho/ipso C−H difunctionalizations of aromatic compounds were designed to afford polyfunctionalized arenes including challenging 1,2,3,4‐tetrasubstituted ones (62 examples, up 97 % yields). To ensure the excellent regioselectivity process while keeping high efficiency, an original strategy based on a “C−H thianthenation/Catellani‐type reaction” sequence was developed starting from simple arenes. Non‐prefunctionalized first regioselectively converted into corresponding thianthrenium salts. Then, palladium‐catalyzed, norbornene (NBE)‐mediated allowed synthesis ipso ‐olefinated/ ortho ‐alkylated using thianthrene as leaving group (revisited Catellani reaction). Pleasingly, commercially available (NBE) and unique catalytic system, synthetic challenges known for reaction with aryl iodides smoothly successfully tackled “thianthrenium” approach. The protocol robust (gram‐scale reaction) widely applied two‐fold functionalization various bio‐active compounds. Moreover, panel olefins alkyl halides coupling partners suitable. further incorporation other groups at (CN/alkyl/H, aryl) (alkyl, aryl, amine, thiol) positions, showcasing generality process.
Язык: Английский
Процитировано
5
Chemical Communications, Год журнала: 2024, Номер 60(76), С. 10552 - 10555
Опубликована: Янв. 1, 2024
We report boron-intermediary ligand transfer of diaryliodonium salt, synthesizing polyfluorolalkyl aryl ethers in the absence transition metal catalyst or base.
Язык: Английский
Процитировано
3
Molecules, Год журнала: 2025, Номер 30(2), С. 236 - 236
Опубликована: Янв. 9, 2025
Orthopalladated derivatives from substituted phenylglycines [Pd(μ-Cl)(C6H3R1C(R2)(R3)N(R4)2]2 (1) react with halogenating reagents (PhICl2, Br2, I2) (2) to give the corresponding o-halogenated amino acids C6H3(X)R1C(R2)(R3)N(R4)2 (3). The reaction is general and tolerates a variety of functional groups (R1 R4) at aryl ring, Cα, N atom. On other hand, PhI(OAc)2 in presence alcohols R5OH (4) gives o-alkoxylated C6H3(OR5)R1C(R2)(R3)N(R4)2 (5), also as process. A partial loss enantiomeric excess observed when starting phenylglycine enantiomerically pure, this arising formation bridging azavinylidene (6) imine intermediate species (7), which were characterized by X-ray diffraction methods.
Язык: Английский
Процитировано
0
Comptes Rendus Chimie, Год журнала: 2025, Номер 28(G1), С. 27 - 35
Опубликована: Фев. 13, 2025
In the quest for molecular complexity, direct and selective functionalization of C(sp3) centers is paramount importance. As sulfur- and/or fluorine-containing molecules are particularly important, development methods to (regio)selectively introduce moieties containing these atoms on a center by C–H bond or decarboxylative reaction has garnered our interest in last few years. Given challenges that represents, this account summarizes recent contributions thanks strategies based transition metal catalysis photochemistry. La fonctionnalisation directe et sélective de centres est une approche remarquable permettant d'obtenir des molécules complexes façon efficace. Du fait l'importance contenant du soufre et/ou fluor, le développement méthodes pour introduire (régio)sélectivement groupements ces atomes sur un centre C(sp3), par d'une liaison ou réaction décarboxylante, suscité vif intérêt au cours dernières années. Étant donné les défis que représente la cet article résume nos récentes grâce à stratégies basées catalyse métaux photochimie.
Процитировано
0
European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(8)
Опубликована: Янв. 8, 2024
Abstract Organic thiocyanates are an important class of compounds because they present in several bioactive molecules and can be used as key synthetic intermediates to access biorelevant sulfur‐containing scaffolds. Although the chemistry organothiocyanates has been studied for decades, a recent resurgence interest field led major advances synthesis new bearing thiocyanate moiety. An emerging powerful strategy consists selective functionalization C(sp 3 )‐H bonds through formation C‐centered radical intermediate. This review highlights work that reported novel alkylthiocyanate scaffolds this promising approach.
Язык: Английский
Процитировано
1
ChemistryEurope, Год журнала: 2024, Номер 2(5)
Опубликована: Авг. 13, 2024
Abstract Herein, we describe the trifluoro‐ and difluoroethoxylation of C(sp 2 )‐H bonds using nickel(II) complexes incorporating a model macrocyclic arene substrate. Due to coordinative properties substrate, were able detect characterize just‐formed )−OCH CF 3 −Ni(II) species by HRMS IRPD. DFT studies on bond formation mechanism indicate that it involves Ni(III)/Ni(I) reductive elimination followed oxidation Ni(II) rather than higher energy barrier Ni(IV)/Ni(II) elimination. This mechanistic investigation deepens versatile redox abilities Ni compounds might help in designing new catalysts for 2,2,2‐trifluoroethoxylation 2,2‐difluoroethoxylation C−H bonds.
Язык: Английский
Процитировано
1
Chemistry - A European Journal, Год журнала: 2023, Номер 30(8)
Опубликована: Дек. 14, 2023
Abstract Herein, we report the Cu‐complex catalyzed, native functional group‐assisted, and TFA/NMF additives promoted (phenylsulfonyl)difluoromethylation of vinylic C(sp 2 )−H bond acrylamides. Using our in‐home designed reagent, this reaction enables construction )−CF SO Ph from simple C−H activation by copper catalysis under mild conditions with total Z ‐selectivity. The versatility utilized fluorinated group was illustrated its conversion into value‐added CF moieties as well remarkable =CHF residue. performed experimental computational mechanistic studies enabled to identify true nature active catalyst substrate, establish critical roles TFA NMF additives. In reaction, acts a promoter much‐needed Cu II /Cu →Cu III I disproportionation, while facilitates following ligand exchange C−C coupling processes. We ruled out generation radical intermediates established be irreversible rate‐determining step entire process.
Язык: Английский
Процитировано
3
Angewandte Chemie, Год журнала: 2024, Номер 136(30)
Опубликована: Май 7, 2024
Abstract Site‐selective ortho/ipso C−H difunctionalizations of aromatic compounds were designed to afford polyfunctionalized arenes including challenging 1,2,3,4‐tetrasubstituted ones (62 examples, up 97 % yields). To ensure the excellent regioselectivity process while keeping high efficiency, an original strategy based on a “C−H thianthenation/Catellani‐type reaction” sequence was developed starting from simple arenes. Non‐prefunctionalized first regioselectively converted into corresponding thianthrenium salts. Then, palladium‐catalyzed, norbornene (NBE)‐mediated allowed synthesis ipso ‐olefinated/ ortho ‐alkylated using thianthrene as leaving group (revisited Catellani reaction). Pleasingly, commercially available (NBE) and unique catalytic system, synthetic challenges known for reaction with aryl iodides smoothly successfully tackled “thianthrenium” approach. The protocol robust (gram‐scale reaction) widely applied two‐fold functionalization various bio‐active compounds. Moreover, panel olefins alkyl halides coupling partners suitable. further incorporation other groups at (CN/alkyl/H, aryl) (alkyl, aryl, amine, thiol) positions, showcasing generality process.
Язык: Английский
Процитировано
0
Chemistry of Heterocyclic Compounds, Год журнала: 2024, Номер 60(5-6), С. 299 - 303
Опубликована: Июнь 1, 2024
Язык: Английский
Процитировано
0