Fluorinated heterocycles play an important role in pharmaceutical and agrochemical industries. Herein, we report on the synthesis of four types fluorinated via rhodium(III)-catalyzed C—H activation arenes/alkenes versatile coupling with 2,2-difluorovinyl tosylate. With N-OMe benzamide being a directing group (DG), reaction delivered monofluorinated alkene retention tosylate functionality. Subsequent one-pot acid treatment allowed efficient 4-fluoroisoquinolin-1(2H)-ones...

Bicyclo[2.1.1]hexanes (BCHs) represent an intriguing class of structurally rigid hydrocarbons that can serve as the bioisosteres benzenoids in medicinal chemistry. Methods for synthesis BCHs are, however, limiting. Reported herein is a facile via strain-release-driven [2π + 2σ] cycloaddition bicyclo[1.1.0]butanes (BCBs) with alkenes facilitated by pyridine-boryl radical catalyst. The mild reaction conditions, broad substrate scope, and decent functional group tolerance this protocol render...

The first Pd-catalyzed method for direct olefination at the C4 position of tryptophan derivatives has been developed via C–H activation to prepare 4-substituted tryptophans, which could be used synthesis many hemiterpenoid indole alkaloids. This reaction proceeds under mild conditions and with exceptional tolerance a variety functional groups. Furthermore, efficiency this is demonstrated by rapid biomimetic clavicipitic acid.

A tandem Cp*Rh(III)-catalyzed C–H activation/Brønsted acid-catalyzed intramolecular cyclization allows a facile synthesis of carbazoles from readily available indoles. The reaction proceeds under rather mild conditions with the generation water and N2 as only byproducts. Broad substrate scope, excellent functional group tolerance, high yields were observed. benzannulation pyroles for indoles is also feasible using same protocol.

Abstract Heteroarenes are important structural motif in functional molecules. A Mn I ‐catalyzed 1,2‐diheteroarylation of allenes via a C−H activation/Smiles rearrangement cascade is presented. The reaction occurred under additive‐free or even solvent‐free conditions, which allowed the creation two C−C and one C−N bonds single operation. series structurally diverse bicyclic tricyclic compounds bearing an exocyclic double bond were constructed good to excellent efficiency. decarboxylative...

Cp*Co(III)-catalyzed annulations of 2-alkenylphenols with CO for the synthesis coumarin derivatives have been developed. The reaction features mild conditions, broad substrate scope, and good functional group tolerance. Preliminary mechanistic studies were conducted, suggesting that C–H activation is turnover limiting step. Furthermore, efficiency this was demonstrated by rapid total three natural products herniarin, xanthyletin, seselin.

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.

A reductive cross-coupling of gem-difluoroalkenes with diverse unactivated and heteroatom substituted olefins through a Fe-catalyzed hydrogen atom transfer (HAT) strategy is reported. Different from the previous HAT-type olefin reactions, presence fluorine in molecule results stereoselective β-F cleavage, leading to C(sp2)–C(sp3) bond formation. wide variety alkylated monofluoroalkenes were obtained good efficiency excellent Z selectivity under air- water-tolerant reaction conditions....

Abstract A cobalt‐catalyzed decarboxylative Negishi coupling reaction of redox‐active aliphatic esters with organozinc reagents was developed. The method enabled efficient alkyl–aryl, alkyl–alkenyl, and alkyl–alkynyl reactions under mild conditions no external ligand or additive needed. success an in situ activation protocol the facile synthesis drug molecule (±)‐preclamol highlight synthetic potential this method. Mechanistic studies indicated that a radical mechanism is involved.

Abstract The introduction of trifluoromethyl groups into organic molecules is paramount importance in modern synthetic chemistry and medicinal chemistry. While methods for constructing C(sp 2 )−CF 3 bonds have been well established, the advancement practical comprehensive approaches forming remains considerably restricted. In this work, we describe an efficient site‐specific deaminative trifluoromethylation reaction aliphatic primary amines to afford corresponding alkyl compounds. proceeds...

A general method to convert simple exocyclic alkenes (no Ar‐substituents) into saturated F2‐rings has been developed. The reaction involves the IIII‐reagent C6F5I(OAc)2 (F5‐PIDA). efficiently works on mg‐, g‐, and even multigram scale.

A concise total synthesis of lamellarins D (7 steps), H and R (5 steps) ningalin B is achieved starting from the corresponding aldehydes amines. The features three oxidative reactions as key steps in a biomimetic manner, involving an AgOAc-mediated coupling reaction to construct pyrrole core, Pb(OAc)4-induced cyclization form lactone, Kita's oxidation pyrrole−arene C−C bond.

A simple and efficient method for the synthesis of 1,3,4-trisubstituted or 3,4-disubstituted pyrroles has been developed. The reaction represents first time that are synthesized directly from readily available aldehydes amines (anilines) as starting materials. This successfully applied to rapid purpurone.

Cp*Rh(<sc>iii</sc>)- and Cp*Ir(<sc>iii</sc>)-catalysed direct C–H arylation with quinone diazides provides a facile redox-neutral access to arylated phenols.

A redox-neutral bimetallic Rh(iii)/Ag(i) relay catalysis allowed the efficient construction of 3-alkylidene isoindolinones and isobenzofuranones. The Rh(iii) catalyst was responsible for C-H monofluoroalkenylation reaction, whereas Ag(i) salt an activator follow-up cyclization. methodology developed applied as a key step in rapid total synthesis natural product aristolactam BII.

Polysubstituted allyl groups, for example, the prenyl group, are valuable synthetic handles and widely encountered in bioactive compounds. Reported herein is a manganese(I)-catalyzed direct C–H coupling with allenes efficient assembly of allylated arenes. The protocol offers an extremely high level atom-economy particularly suited introduction 1,1-disubstitiuted as exemplified by quantitative syntheses variety prenylated indoles. practicality this method was evidenced gram-scale synthesis...

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 In this study, a Mn I /Ag ‐based relay catalysis process is described for the one‐pot synthesis of polycyclic products by formal [3+2] and [4+2] cycloaddition reaction cascade. A manganese(I) complex catalyzed first example directed C−H allylation with allenes, setting stage an in situ Povarov cyclization silver(I). The proceeds high bond‐forming efficiency (three C−C bonds), broad substrate scope, regio‐ stereoselectivity, 100 % atom economy.

Abstract A synthetic method for isoquinoline synthesis via a [4+2] annulation of NH imines with alkynes using the high‐valent (pentamethylcyclopentadienyl)cobalt(III) [Cp*Co(III)] catalyst is described. Cerium(IV) sulfate was found to be an efficient oxidant in lieu commonly used copper or silver salts. Broad substrate scope, high functional group tolerance, and generally good yields were observed. magnified image

Group 9 Cp*M(III) (M = Co, Rh, Ir) complexes have been extensively investigated as catalysts in a variety of C–H activation reactions. Typically, late metal-based silver or copper salt was used (while needed) oxidant these catalytic systems. Herein, we report our discovery potentially general type N–O bond-containing oxidants, which allowed the mild and efficient syntheses isocoumarins, isoquinolines, isoquinolinone, styrenes via catalyzed by group complexes. By using Cp*Rh(III)-catalyzed...

Abstract Heteroarenes are important structural motif in functional molecules. A Mn I ‐catalyzed 1,2‐diheteroarylation of allenes via a C−H activation/Smiles rearrangement cascade is presented. The reaction occurred under additive‐free or even solvent‐free conditions, which allowed the creation two C−C and one C−N bonds single operation. series structurally diverse bicyclic tricyclic compounds bearing an exocyclic double bond were constructed good to excellent efficiency. decarboxylative...