Give Me an Ar, give N! Arylation of the methyl group in a simple derivative readily available alanine under palladium catalysis was followed by intramolecular amidation at same position to chiral α-amino-β-lactams with wide range aryl substituents (see scheme; Phth=phthaloyl). The were obtained moderate high yields good functional-group tolerance and diastereoselectivity. As service our authors readers, this journal provides supporting information supplied authors. Such materials are peer...

Recent advances in copper-mediated (both stoichiometric and catalytic) chelation-assisted functionalization of unactivated C–H bonds are reviewed.

Most chelation-assisted aliphatic C-H activation proceeds through a kinetically favored five-membered cyclometalated intermediate. Here, we report the first site-selective alkenylation of δ-C(sp(3))-H in presence more accessible γ-C(sp(3))-H bonds via less six-membered palladacycle. A wide range functional groups are tolerated, and unique protocol can be applied to synthesis chiral piperidines. Moreover, mechanistic insights have been conducted elucidate origin unusual site-selectivity.

A copper-catalyzed direct sulfonylation of C(sp2)–H bonds with sodium sulfinates using a removable directing group is described. This reaction tolerates wide range functional groups, providing an efficient protocol for the synthesis diverse aryl sulfones. Moreover, series 2,6-disubstituted benzamides could be synthesized via sequential C–H functionalization.

A Pd(II)-catalyzed sulfonylation of unactivated C(sp3)–H bonds with sodium arylsulfinates using an 8-aminoquinoline auxiliary is described. This reaction demonstrates excellent functional group tolerance respect to both the caboxamide starting material and arylsulfinate coupling partner, affording a broad range aryl alkyl sulfones. Moreover, late-stage modification complex molecules was achieved via this protocol.

Katalyse mit Folgen: Die Palladium-katalysierte Arylierung der Methylgruppe in einem einfachen Alaninderivat anschließender intramolekularer Amidierung an gleicher Position ergibt chirale α-Amino-β-lactame einer Bandbreite von Arylsubstituenten (siehe Schema; Phth=Phthaloyl). wurden mittleren bis hohen Ausbeuten und Diastereoselektivitäten erhalten, funktionelle Gruppen gut toleriert. As a service to our authors and readers, this journal provides supporting information supplied by the...

A catalyst-controlled vicinal amino- versus oxy-acetoxylation of alkenes with PhI(OAc)2 as the oxidant is described. The divergent synthesis cyclic ureas and isoureas was achieved in good yields under mild conditions employing ambident urea nucleophiles. Both terminal internal are compatible this reaction protocol.

A practical and efficient method for selective intramolecular radical trifluoromethylacylation -arylation of alkenes with inexpensive CF3SO2Na K2S2O8 in aqueous media has been developed, respectively, affording the highly chemoselective synthesis CF3-functionalized chroman-4-ones chromanes satisfactory yields. Control experiments DFT calculations indicate that CF3SO2Na/K2S2O8 system is capable trifluoromethylating substrate without a transition metal catalyst oxidation to ·CF3 by involved...

Purine is utilized as a new directing group for the Pd-catalyzed monoarylation of 6-arylpurines with simple aryl iodides via C−H bond activation in good yields, providing complementary tool modification (nucleosides). Most importantly, purine can be used building block nucleoside derivatives, and use helps avoid additional synthetic steps.

A copper-catalyzed direct aminosulfonylation of unactivated alkenes with sodium sulfinates for the efficient synthesis sulfonylated pyrrolidones is described. This reaction features good functional group tolerance and wide substrate scope, providing an straightforward protocol to access this kind pyrrolidones. Moreover, preliminary mechanistic investigations disclosed that a free-radical pathway might be invovled in process.

A nickel-catalyzed direct sulfonylation of alkenes with sulfonyl chlorides has been developed using 1,10-phenanthroline-5,6-dione as the ligand. Unactivated and styrenes including 1,1-, 1,2-disubstituted can be subjected to protocol, a wide range vinyl sulfones was obtained in high excellent yields good functional group compatibility. Notably, process did not allow desulfonylation chloride or chlorosulfonylation alkenes. Radical-trapping experiment supported that free-radical likely produced...

A novel and efficient method for the intermolecular hydroxysulfonylation of vinylarenes using sodium sulfinates has been achieved through aerobic copper catalysis. This transformation proceeded smoothly with green air as terminal oxidant in presence Cu (I)/1,10-phenanthroline an catalytic system, leading to array β-hydroxysulfones moderate high yields. The significant advantages this protocol are mild reaction conditions, readily available starting materials, good functional-group...

A highly regioselective Pd-catalyzed C(Ar)-H bond activation method was developed for the modification of purines (nucleosides) with different functional groups by using purine as a directing group. This approach provides new access to variety functionalized which are potentially great importance in medicinal chemistry.

A novel protocol for a Cu-catalyzed direct C(sp2)–H activation/intramolecular amination reaction of 6-anilinopurine nucleosides has been developed. This approach provides new access to variety multiheterocyclic compounds from purine via intramolecular N–H bond tautomerism which are endowed with fluorescence.

A simple and practical photochemical strategy for intermolecular perfluoroalkyl-alkenylation of alkenes with 2-amino-1,4-naphthoquinones perfluoroalkyl iodides has been demonstrated under visible-light irradiation. Mechanistic studies reveal that easily available 2-amino-1,4-naphthoquinone substrates can serve as efficient photosensitizers to activate through a photoredox process. Therefore, the developed radical relay reaction proceeds smoothly without additional transition metals photocatalysts.

A visible-light photoredox-catalyzed sulfonyl lactonization of unsaturated carboxylic acids with chlorides is described. This reaction features good functional group tolerance and a broad substrate scope, providing simple efficient protocol to access wide range lactones in high excellent yields. Preliminary mechanistic investigations suggested that free-radical pathway should be involved the process.

Pd(<sc>ii</sc>)-Catalyzed direct C(sp³)–H germylation of α-AA derivatives with the assistance a bidentate auxiliary for efficient synthesis β-germyl-α-amino amides is reported.

By altering the amount of Selectfluor, highly selective mono- and difluorination 1,3-dicarbonyl compounds has been achieved, affording a variety 2-fluoro- 2,2-difluoro-1,3-dicarbonyl in good to excellent yields. The reaction can be readily performed aqueous media without any catalyst base, which features practical convenient fluorination. Importantly, gram-scale reaction, transformation 2-fluoro-1,3-diphenylpropane-1,3-dione 4-fluoro-1,3,5-triphenyl-1H-pyrazole, chlorination bromination are...

An aerobic copper-catalyzed oxysulfonylation of vinylarenes with sodium sulfinates is described. This protocol features mild reaction conditions, convenient operation, and broad substrate scope respect to sulfinates. Notably, the demonstrates excellent tolerance functional groups such as chloro, bromo, ester, cyano, nitro groups. Mechanistic investigations indicated that should undergo radical cascades involving a sulfonyl generated from sulfinate air terminal oxidant, addition across alkene...

A Pd-catalyzed high regioselective diarylation of 9-allyl-9H-purinevia chelation-assisted Heck reaction is developed. There were two different types β-H in the allyl substrate, while aryl groups are exclusively introduced to terminal olefins.

An acyl lactonization of alkenes with aldehydes under visible-light photoredox catalysis is described. With the protocol, a broad scope alkenoic acids and could be compatible good functional group tolerance obtained. A series lactones are obtained isolated yields ranging from 50–95%. Mechanistic studies revealed that transformation should proceed via radical chain process.

Abstract A photocatalytic acyl lactonization of unsaturated carboxylic acids using simple and inexpensive chlorides has been developed for a modular synthesis lactones. Significantly, the protocol could allow an efficient construction biologically important phthalide framework. The transformation be extended to wide variety acids, including substituted 2‐vinyl benzoic different types alkenoic acids. Moreover, series aroyl, heteroaroyl serve as coupling partners. Notably, functional groups...

Abstract A decarboxylation‐triggered and o ‐hydroxyl‐controlled hydrogen‐transfer strategy for the one‐pot synthesis of benzoxazoles from readily available amino acids 2‐nitrophenols is reported. On basis this autoredox reaction, C−N bond can be efficiently constructed to afford desired products in moderate good yields under transition‐metal‐free conditions aqueous media. magnified image