The linear or branched allyl moieties on aromatic rings are well-known as ubiquitous structural motifs found in a range of natural products and medicinally relevant molecules. They also represent an important class organic intermediates for the transformation olefin group into many useful functional groups. Established methods installation allylic groups rely primarily nucleophilic substitution transmetalation aryl metal complexes to electrophiles, Lewis acid-mediated Friedel–Crafts...

The rhodium-catalyzed oxidative acylation between secondary benzamides and aryl aldehydes via sp2 C–H bond activation followed by an intramolecular cyclization is described. This method results in the direct efficient synthesis of 3-hydroxyisoindolin-1-one building blocks.

A mild, practical and efficient palladium-catalyzed decarboxylative ortho-acylation of O-methyl ketoximes with α-keto acids via C-H bond activation is described. In these reactions, a broad range undergoes the cross-coupling reactions high selectivities good tolerance.

A palladium-catalyzed decarboxylative acylation of phenylacetamides with α-oxocarboxylic acids via C-H bond activation is described. This protocol provides efficient access to a range ortho-acyl phenylacetamides, which can be easily converted 3-isochromanone derivatives.

The rhodium(III)-catalyzed direct C–H functionalization of azobenzenes with α-diazo compounds is described. These transformations provide the facile and efficient construction C2-alkylated or highly substituted cinnolin-3(2H)-ones. Furthermore, this protocol leads to formation cinnolin-3(2H)-ones using a diazo derivative Meldrum’s acid.

Palladium-catalyzed decarboxylative acylation of highly substituted indolines with α-keto acids via C–H bond activation is described. This protocol provides efficient access to C7-carbonylated indoles known have diverse biological profiles.

The rhodium(<sc>iii</sc>)-catalyzed direct functionalization of aniline C–H bonds with α-diazo compounds for the preparation <italic>ortho</italic>-alkylated anilines and highly substituted indoles is described.

The rhodium(III)-catalyzed cross-coupling reaction of 8-methylquinolines and maleimides is described. In contrast to the C(sp2)–H functionalization, a first catalytic functionalization sp3 C–H bonds with reported. This protocol provides facile access various succinimide scaffolds on via direct cleavage approach.

The rhodium(III)-catalyzed redox-neutral coupling reaction of N-acyl ketimines generated in situ from 3-hydroxyisoindolinones with various activated olefins is described. This approach leads to the synthesis bioactive spiroisoindolinone derivatives moderate high yields. In case internal such as maleimides, maleates, fumarates, and cinnamates, spiroindanes were obtained by [3 + 2] annulations reaction. sharp contrast, acrylates quinones displayed β-H elimination followed Prins-type...

Abstract The rhodium‐catalyzed selective cyanation of CH bonds indolines and indoles with N ‐cyano‐ ‐phenyl‐ para ‐methylbenzenesulfonamide is described. This protocol offers a facile access to C‐7 cyanated C‐2 high site selectivity excellent functional group tolerance. magnified image

The weakly coordinating ketone group directed C–H functionalizations of chromones, 1,4-naphthoquinones, and xanthones with various maleimides under rhodium(III) catalysis are described. These protocols efficiently provide a range succinimide-containing naphthoquinones, excellent site selectivity functional compatibility. All synthetic compounds were screened for in vitro anticancer activity against human breast adenocarcinoma cell lines (MCF-7). In particular, 7aa 7ca naphthoquinone scaffold...

The rhodium(III)-catalyzed direct C-H functionalization of various indolines with 1,4,2-dioxazol-5-ones as new amidating agents is described. This transformation provides efficient preparation C7-amidated known to display potent anticancer activity. synthetic compounds were evaluated for in vitro activity against human prostate adenocarcinoma cells (LNCaP), endometrial (Ishikawa), and ovarian carcinoma (SKOV3). Compound 4f was found be highly cytotoxic, competitive that agent doxorubicin.

The rhodium(III)-catalyzed direct C–H functionalization of azobenzenes with ethyl glyoxalate and aryl glyoxals is described. This protocol provides the facile efficient formation various C3-acylated-(2H)-indazoles in moderate to high yields.

The ruthenium-catalyzed oxidative allylation of aromatic and α,β-unsaturated carboxamides with allylic carbonates is described. These transformations proceed readily complete linear γ-selectivity substituted carbonates.

The rhodium(III)-catalyzed direct allylation of indolines with allylic carbonates at room temperature is described. These transformations provide the facile and efficient construction C7-allylated indolic scaffold.

The rhodium(III)-catalyzed direct cross-coupling reaction of electron-deficient acrylamides with maleimides is described. This protocol displays broad functional group tolerance and high efficiency, which offers a new opportunity to access highly substituted succinimides. Dependent on the substituent positions conditions, olefin migrated products were obtained regio- stereoselectivity.

A mild and efficient approach for the cross-coupling reaction of 8-methylquinolines with a range allylic alcohols in water as solvent under rhodium(<sc>iii</sc>) catalysis is described.

Abstract The palladium‐catalyzed oxidative acylation of indolines at the C‐7 position with aldehydes or alcohols via CH bond activation is described. This protocol represents a facile access to 7‐acylated indolines, which can be readily transformed into indoles diverse biological properties. magnified image

The rhodium(III)-catalyzed site-selective C-H alkylation of various N-heterocycles, such as indolines, carbazoles, and pyrroles with readily available allylic alcohols is described. This protocol allows the generation a heterocyclic scaffold containing β-aryl carbonyl moiety, which known to be crucial structural unit biologically active compounds.

Abstract The ruthenium(II)‐ or rhodium(III)‐catalyzed pyrimidinyl‐directed Grignard‐type C−H additions of N‐heterocycles with activated aldehydes and ketones are described. A cationic ruthenium catalyst sodium acetate additive in dichloroethane as solvent were found to be optimal catalytic system for the construction C‐7 alkylated indolines. In sharp contrast, a rhodium complex allows generation C‐2 indoles pyrroles well C‐1 carbazoles. site‐selective functionalization these heterocyclic...

The pyrimidinyl-directed C–H functionalization of indolines with anthranils as amination sources under rhodium(<sc>iii</sc>) catalysis is described to afford a range C7-aminated indoline derivatives excellent site-selectivity and functional group compatibility.

This review focuses on the advances in transition-metal catalyzed reactions with fluorinated building blocks via directed C–H bond activation for construction of diverse organic molecules an insight into probable mechanistic pathway.

Abstract A palladium‐catalyzed ortho ‐acylation of N ‐benzyltriflamides with aldehydes via direct sp 2 CH bond activation is described. Benzylamines a triflamide directing group in the presence palladium acetate, acetic acid, and tert ‐butyl hydroperoxide as an oxidant can be effectively coupled aryl alkyl to provide ‐acyl‐ high regioselectivity.