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 1d−l, benzylic 1m−u furnish products carbonyl allylation 3a−u with exceptional levels asymmetric induction. The very same set optically enriched are accessible enals 2a−c, aldehydes 2d−l, aryl 2m−u, using catalysts ligated by (−)-TMBTP...

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...

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 presence an iridium catalyst derived [IrCl(cod)]2 and (R)-BINAP delivers products C-allylation 2a-i. Employing isopropanol as terminal reductant, exposure aryl aldehydes 3a-i (-)-TMBTP identical In all cases examined, exception levels enantioselectivity observed. Thus, is...

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 chiral phosphine ligand (S)-SEGPHOS, α-methyl allyl acetate couples to alcohols 1a−1j with complete levels branched regioselectivity furnish products carbonyl crotylation 3a−3j, which are formed good anti-diastereoselectivity exceptional enantioselectivity. An identical set optically enriched 3a−3j is accessible corresponding...

Unstable? We're able! 1,n-Glycols serve as synthetic equivalents to unstable dialdehydes in two-directional carbonyl allylation from the alcohol oxidation level under iridium-catalyzed transfer hydrogenation conditions. Iterative asymmetric employing 1,3-propanediol enables rapid assembly of protected 1,3-polyol substructures with exceptional levels stereocontrol.

Enantioselective transfer hydrogenation of 1,1-dimethylallene 1a in the presence aromatic, alpha,beta-unsaturated, or aliphatic aldehydes 2a-i mediated by 2-propanol and employing a cyclometalated iridium C,O-benzoate derived from allyl acetate, m-nitrobenzoic acid, (S)-SEGPHOS delivers reverse-prenylation products 4a-i good to excellent isolated yields (65-96%) enantioselectivities (87-93% ee). In absence 2-propanol, enantioselective carbonyl reverse prenylation is achieved directly alcohol...

A rhodium-catalyzed oxidative acylation of benzamides with aryl aldehydes via direct sp2 C–H bond cleavage is described. In the presence [Cp*RhCl2]2, AgSbF6, and silver carbonate as an oxidant, N,N-diethyl can be effectively carbonylated to yield ortho-acyl benzamides.

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.

Two novel nano-cage compounds, 8 and 9, were prepared by self-assembly of the ruthenium complexes 4 5, tripodal donor 1. The cytotoxicity was found to be considerably stronger than that cisplatin. complex inhibited tumor cell proliferation interfering into regulatory pathways cycleviaapoptosis.

A total synthesis of the oxo-polyene macrolide (+)-roxaticin is achieved in 20 steps from 1,3-propanediol. In this approach, 9 10 C−C bonds formed longest linear sequence are made via metal catalysis, including 7 by iridium catalyzed alcohol coupling. Notably, present synthesis, which represents most concise preparation any reported to date, absence chiral reagents and auxiliaries with minimal use premetalated C-nucleophiles.

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...

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 (2H)-indazoles with a range substrate scope. A high level chemoselectivity functional group tolerance this transformation were also observed.

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.