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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 of organic intermediates for the transformation of an olefin group into many useful functional groups. Established methods for the installation of allylic groups rely primarily on nucleophilic substitution or transmetalation of aryl metal complexes to allyl electrophiles, Lewis acid-m

Under the conditions of transfer hydrogenation employing an iridium catalyst generated in situ from [Ir(cod)Cl]2, chiral phosphine ligand (R)-BINAP or (R)-Cl,MeO-BIPHEP, and m-nitrobenzoic acid, allyl acetate couples to allylic alcohols 1a-c, aliphatic alcohols 1d-l, and benzylic alcohols 1m-u to furnish products of carbonyl allylation 3a-u with exceptional levels of asymmetric induction. The very same set of optically enriched carbonyl allylation products 3a-u are accessible from enals 2a-c, al

Protocols for highly enantioselective carbonyl allylation from the alcohol or aldehyde oxidation level are described based upon transfer hydrogenative C-C coupling. Exposure of allyl acetate to benzylic alcohols 1a-i in the presence of an iridium catalyst derived from [IrCl(cod)]2 and (R)-BINAP delivers products of C-allylation 2a-i. Employing isopropanol as terminal reductant, exposure of allyl acetate to aryl aldehydes 3a-i in the presence of an iridium catalyst derived from [IrCl(cod)]2 and (

Under the conditions of transfer hydrogenation employing an ortho-cyclometallated iridium catalyst generated in situ from [Ir(cod)Cl](2), 4-cyano-3-nitrobenzoic acid and the chiral phosphine ligand (S)-SEGPHOS, alpha-methyl allyl acetate couples to alcohols 1a-1j with complete levels of branched regioselectivity to furnish products of carbonyl crotylation 3a-3j, which are formed with good levels of anti-diastereoselectivity and exceptional levels of enantioselectivity. An identical set of optica

A rhodium-catalyzed oxidative acylation of benzamides with aryl aldehydes via direct sp(2) C-H bond cleavage is described. In the presence of [Cp*RhCl(2)](2), AgSbF(6), and silver carbonate as an oxidant, N,N-diethyl benzamides can be effectively carbonylated to yield ortho-acyl benzamides.

The rhodium-catalyzed oxidative acylation between secondary benzamides and aryl aldehydes via sp(2) C-H bond activation followed by an intramolecular cyclization is described. This method results in the direct and 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 of O-methyl ketoximes and α-keto acids undergoes the decarboxylative cross-coupling reactions with high selectivities and 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 of ortho-acyl phenylacetamides, which can be easily converted to 3-isochromanone derivatives.

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 of bioactive spiroisoindolinone derivatives in moderate to high yields. In the case of internal olefins such as maleimides, maleates, fumarates, and cinnamates, spiroindanes were obtained by the [3 + 2] annulations reaction. In sharp contrast, acrylates and quinones displayed the β-H elimina

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

The rhodium(III)-catalyzed direct functionalization of aniline C-H bonds with α-diazo compounds is described. These transformations provide a facile construction of ortho-alkylated anilines with diazo malonates or highly substituted indoles with diazo acetoacetates.

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 to have diverse biological profiles.

The rhodium(III)-catalyzed cross-coupling reaction of 8-methylquinolines and maleimides is described. In contrast to the C(sp(2))-H functionalization, a first catalytic functionalization of sp(3) C-H bonds with maleimides is reported. This protocol provides a facile access to various succinimide scaffolds on 8-methylquinolines via a direct C-H cleavage approach.

The rhodium(III)-catalyzed C-H functionalization followed by intramolecular annulation reactions between azobenzenes and sulfoxonium ylides is described. This protocol leads to the efficient formation of 3-acyl (2 H)-indazoles with a range of substrate scope. A high level of chemoselectivity and functional group tolerance of this transformation were also observed.