The first copper-catalyzed direct β-functionalization of saturated ketones is reported. This protocol enables diverse to couple with a wide range nitrogen, oxygen and carbon nucleophiles in generally good yields under operationally simple conditions. detailed mechanistic studies including kinetic studies, KIE measurements, identification reaction intermediates, EPR UV–visible experiments were conducted, which reveal that this proceeds via novel radical-based dehydrogenation enone subsequent...

Direct: With [Pd2(dba)3] as a catalyst, the direct alkynylation of thiophenes bearing variety substituents has been accomplished by using terminal alkynes alkynylating reagents. This protocol is also applicable to other electron-rich aromatic heterocycles. dba=dibenzylidenacetone. As service our authors and readers, this journal provides supporting information supplied authors. Such materials are peer reviewed may be re-organized for online delivery, but not copy-edited or typeset. Technical...

Acid to acid: A general method has been developed for the synthesis of biaryl compounds through a decarboxylative cross-coupling reaction between two different (hetero)aryl carboxylic acids (see scheme). The use PdII/PCy3 catalyst enables electronically or similar aryl acids. This is compatible with substrates having nitro, cyano, fluoro, chloro, bromo, trifluoromethyl, and methoxy substituents. Detailed facts importance specialist readers are published as "Supporting Information". Such...

Rh(III)-catalyzed intermolecular direct aromatic C–H bond amidation with amides has been accomplished under mild reaction conditions. This protocol is applicable to a broad range of N-chelator-containing arenes amidated and aliphatic sulfonamides. A possible mechanism proposed according the experimental results.

Tolerant: By using Pd(OAc)2/PCy3 as a catalyst, both electron-rich aromatic heterocycles and electron-deficient fluorobenzenes undergo the dehydrogenative cross-coupling with (hetero)aryl ethyl ketones in good yields. A broad range of functional groups is tolerated, thus providing general method for facile syntheses chalcones or heterocyclic chalcone analogues. Furthermore, dialkyl can also participate this transformation. Detailed facts importance to specialist readers are published...

Abstract In organic molecules, the reactivity at carbon atom next to functional group is dramatically different from that other atoms. Herein, we report a versatile copper-catalyzed method enables successive dehydrogenation or of ketones, aldehydes, alcohols, α,β-unsaturated diesters, and N -heterocycles furnish stereodefined conjugated dienecarbonyls, polyenecarbonyls, nitrogen-containing heteroarenes. On basis mechanistic studies, process proceeds via initial α,β-desaturation followed by...

A new catalytic methodology has been developed for the synthesis of heteroaryled pyridines via a rhodium(III)-catalyzed dehydrogenative cross-coupling reaction. This protocol features good substrate scope with broad range functional group tolerance and high regioselectivity pyridyl C–H activation.

An efficient Rh/Cu-catalyzed method has been developed for the direct β-arylation or alkenylation of ketones using (hetero)aryl alkenyl carboxylic acids as coupling partners. This ketone β-functionalization reaction proceeded via merging Cu-catalyzed dehydrogenative desaturation and Rh-catalyzed carboxyl-directed C–H alkylation, exhibiting a broad substrate scope both TEMPO proved to be essential dehydrogenation process generation active Rh catalyst activation.

Enamine and imine represent two of the most common reaction intermediates in syntheses, containing α-hydrogen often exhibit similar reactivity to enamines due their rapid tautomerization enamine tautomers. Herein, we report that minor structural difference between tautomer derived from results different chemo- regioselectivity cyclohexanones, amines TEMPO: primary furnishes formal oxygen 1,2-migration product, α-amino-enones, while secondary under conditions generates exclusively arylamines...

Oximes are widely used precursors in synthetic chemistry due to their broad availability and versatile chemical properties, which N‐O bond fragmentation represents a key reactivity mode. However, these transformations typically require the use of oxygen‐protected oximes, general strategy directly utilize free oximes remains challenging vulnerability side reaction pathways, rendering low tendency towards N‐OH cleavage. Here we report unified platform achieve direct cyclization unprotected...

Oximes are widely used precursors in synthetic chemistry due to their broad availability and versatile chemical properties, which N-O bond fragmentation represents a key reactivity mode. However, these transformations typically require the use of oxygen-protected oximes, general strategy directly utilize free oximes remains challenging vulnerability side reaction pathways, rendering low tendency towards N-OH cleavage. Here we report unified platform achieve direct cyclization unprotected...

Herein, we disclose a metal-free, operationally simple, general method for straightforward syntheses of catechols via α-oxygenation cyclohexanone initiated cascade oxidative reaction sequence. This metal-free is particularly advantageous for...

Direkt: Mit [Pd2(dba)3] als Katalysator gelang die direkte Alkinylierung von unterschiedlich substituierten Thiophenen mit terminalen Alkinen Alkinylierungsreagentien. Das Protokoll kann auch für andere elektronenreiche aromatische Heterocyclen verwendet werden. dba=Dibenzylidenaceton. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed may be re-organized for online delivery, but not copy-edited or...

Rh-catalyzed reactions of N-alkyl anilines with internal alkynes at room temperature have been developed using an in situ generated N-nitroso group as a transient oxidizing directing group. Due to mild reaction conditions, this method enabled synthesis broad range indoles, including even two indole-based medicinal compounds. Our work disclosed the feasibility strategy C-H functionalization reactions, which possesses potential enhance overall step-economy and impart new reactivity patterns substrates.

Säure trifft Säure: Bei der hier vorgestellten Synthese von Biarylen durch decarboxylierende Kreuzkupplung (Hetero)arencarbonsäuren (siehe Schema) können elektronisch ähnliche ebenso wie unterschiedliche Arencarbonsäuren miteinander gekuppelt werden. Die Substrate Nitro-, Cyan-, Fluor-, Chlor-, Brom-, Trifluormethyl- oder Methoxysubstituenten tragen. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited...

We report that the direct oxidative cross-coupling of carbonyl compounds with simple alkenes is realized to synthesize α-allylated by identifying bisphosphine ligand BINAP enables copper catalyst integrate two different catalytic cycles in a one-pot system.

Elektronenreiche aromatische Heterocyclen und elektronenarme Fluorbenzole reagieren in Gegenwart des Katalysators Pd(OAc)2/PCy3 einer dehydrierenden Kreuzkupplung mit (Hetero)Arylethylketonen guten Ausbeuten. Verschiedene funktionelle Gruppen werden toleriert, sodass Chalkone heterocyclische Chalkon-Analoga leicht synthetisiert können. Auch Dialkylketone umgesetzt.

A convenient synthesis of α-enaminones from cyclic ketones with anilines at room temperature <italic>via</italic> an oxygen-atom-transfer pathway oxoammonium salt.

Abstract The palladium‐catalyzed direct arylation of polyfluoroarenes with organosilicon reagents was achieved by establishing general reaction conditions. This protocol compatible a broad range functional groups and offered the desired products in moderate to good yields.

Herein, an oxidization reaction of enones with a CuII complex that leads to new type regioselective [3+2] cycloaddition is reported. Highly functionalized cyclopentenes and spirocyclic compounds are obtained in moderate-to-good yields. This occurred through the formation γ-enone radicals, providing rarely explored reactivity pattern for enones.

Polyfunctionalized arenes are privileged structural motifs in both academic and industrial chemistry. Conventional methods for accessing this class of chemicals usually involve stepwise modification phenyl rings, often necessitating expensive noble metal catalysts suffering from low reactivity selectivity when introducing multiple functionalities. We herein report dehydrogenative synthesis

Die direkte Alkinylierung elektronenreicher aromatischer Heterocyclen mit terminalen Alkinen gelang in hohen Ausbeuten und guten Selektivitäten, wenn wenig Palladiumkatalysator verwendet wurde, wie W. Su et al. der Zuschrift auf S. 3718 ff. beschreiben. Eine hohe Katalysatorbeladung führte aufgrund unerwünschten Alkin-Homokupplung zu niedrigen Ausbeuten.

Abstract A convenient and atom‐economic transformation of enones with electron‐deficient alkenes under mild conditions has been developed using DBU as a catalyst. This method utilizes vinylogous strategy to form dienolate intermediates, which provides new approach for the regioselective α‐alkylation enones. protocol exhibits broad range substrate scope good functional group compatibility. Moreover, it enabled formation unexpected cyclic 1,5‐diketone by employing phenyl acrylate Michael...

Abstract The Rh‐catalyzed ortho ‐C(sp 2 )−H functionalization of 8‐aminoquinoline‐derived benzamides with aliphatic acyl fluorides generated in situ from the corresponding acids has been developed. This reaction initiated 8‐aminoquinoline‐directed acylation, which was accompanied by subsequent intramolecular nucleophilic substitution amide group to produce alkylidene phthalides approach exhibits high stereo‐selectivity for Z ‐isomer products, and tolerates a variety functional groups as well...

Abstract The coupling reaction of saturated ketones with nitrogen‐, oxygen‐, and carbon nucleophiles affords the corresponding β‐functionalized ketones.