[RuCl₂(<i>p-</i>cymene)]₂‑Catalyzed Conjugate Addition of Arylboronic Acids to α,β-Unsaturated Ketones under Ligand-Free and Neutral Conditions

A simple and efficient Ru-catalyzed conjugate addition reaction of arylboronic acids to α,β-unsaturated ketones under neutral conditions without any additional ligands has been developed. This Ru­(II)-catalytic system both fulfilled the inhibition of the β-hydride elimination in the catalytic cycle and minimized the protonolysis of arylboronic acids

Enantioselective Synthesis of 1-Aryl-tetrahydroisoquinolines through Iridium Catalyzed Asymmetric Hydrogenation

Asymmetric hydrogenation of 1-aryl-3,4-dihydroisoquinolines using the [IrCODCl]₂/(<i>R</i>)-3,5-diMe-Synphos catalyst is reported. Under mild reaction conditions, this atom-economical process provides easy access to a variety of enantioenriched 1-aryl-1,2,3,4-tetrahydroisoquinoline derivatives, which are important pharmacophores found in several pharmaceutical drug candidates, in high yields and enantiomeric excesses up to 99% after a single crystallization

Diastereo- and Enantioselective Asymmetric Hydrogenation of α‑Amido-β-keto Phosphonates via Dynamic Kinetic Resolution

Dynamic kinetic resolution of various α-amido-β-keto phosphonates via asymmetric hydrogenation proceeded efficiently to give the corresponding β-hydroxy-α-amido phosphonates in high diastereo- and enantioselectivities (up to 99:1 syn/anti, 99.8% ee). The addition of catalytic amounts of CeCl₃·7H₂O is necessary to achieve both good selectivity and catalytic efficiency under mild reaction conditions

Reduction of Benzolactams to Isoindoles via an Alkoxide-Catalyzed Hydrosilylation

An alkoxide-catalyzed reduction of benzolactams to isoindoles with silanes was realized. With <i>t</i>-BuOK as the catalyst and Ph₂SiH₂ as the reductant, a series of benzolactams containing different functional groups were reduced to the corresponding isoindoles, which could be captured by <i>N</i>-phenyl maleimide to form Diels–Alder products in moderate to good yields. Deuterium labeling studies and the hydrosilylation of benzolactam in DMF indicated that the deprotonation of benzolactams took place at C3 potion during the reduction

Ruthenium-Catalyzed Enantioselective Hydrogenation of Ferrocenyl Ketones: A Synthetic Method for Chiral Ferrocenyl Alcohols

Highly effective asymmetric hydrogenation of various ferrocenyl ketones, including aliphatic ferrocenyl ketones as well as the more challenging aryl ferrocenyl ketones, was realized in the presence of a Ru/diphosphine/diamine bifunctional catalytic system. Excellent enantioselectivities (up to 99.8% ee) and activities (S/C = 5000) could be obtained. These asymmetric hydrogenations provided a convenient and efficient synthetic method for chiral ferrocenyl alcohols, which are key intermediates for a variety of chiral ferrocenyl ligands and resolving reagents

Visible-Light-Induced Photocatalytic Aerobic Oxidation/Povarov Cyclization Reaction: Synthesis of Substituted Quinoline-Fused Lactones

A one-step construction of quinoline-fused lactones was achieved by visible-light-induced photocatalytic aerobic oxidation/Povarov cyclization reaction. This method provides a new access to the synthesis of important fused heterocycles under mild reaction conditions

Visible Light-Induced Radical Rearrangement to Construct C–C Bonds via an Intramolecular Aryl Migration/Desulfonylation Process

A highly efficient intramolecular selective aryl migration/desulfonylation of 2-bromo-<i>N</i>-aryl-<i>N</i>-(arenesulfonyl)­amide via visible light-induced photoredox catalysis has been accomplished. This approach allows for the construction of a variety of multisubstituted <i>N</i>,2-diarylacetamide under mild reaction conditions

Palladium-Catalyzed Amidation of Aryl Halides Using 2‑Dialkylphosphino-2′-alkoxyl-1,1′-binaphthyl as Ligands

Palladium-catalyzed intermolecular C–N bond-forming reactions between aryl halides and amides are described using 2-dialkylphosphino-2′-alkoxyl-1,1′-binaphthyl, which is both bulky and electron-rich, as the ligand. A variety of amides, including aliphatic and aromatic primary amides, lactams, and carbamates, were viable substrates for the amidation, which exhibited good functional group compatibility. By tuning the substituents at the 2,2′-position of 1,1′-binaphthyl of the ligand, the palladium-catalyzed amidation of bulky aryl halides was realized and this coupling reaction was used to synthesize 2-amino-2′-methoxy-1,1′-binaphthyl in high yield

Visible-Light-Induced Radical Cascade Cyclization: Synthesis of the ABCD Ring Cores of Camptothecins

A new strategy for constructing indolizino­[1,2-<i>b</i>]­quinolin-9­(11<i>H</i>)-ones (ring cores of camptothecins) from readily available isocyanoarenes and <i>N</i>-(alkyl-2-yn-1-yl)­pyridin-2­(1<i>H</i>)-ones has been developed through a visible-light-induced radical cascade cyclization process. The reaction proceeds under mild conditions with fair to excellent yields. The easy introduction of substituents for both reactants and the broad functional group tolerance of the reaction make it a straightforward route to the cores of the marketed camptothecins and their derivatives

Ruthenium-Catalyzed Oxidation of Allyl Alcohols with Intermolecular Hydrogen Transfer: Synthesis of α,β-Unsaturated Carbonyl Compounds

Ruthenium-catalyzed oxidation of multisubstituted allyl alcohols in the presence of benzaldehyde gives enals or enones in good yields. Unlike the commonly reported ruthenium-catalyzed isomerization reaction of allyl alcohols to give saturated ketones, an intermolecular rather than intramolecular hydrogen transfer is involved in this transformation. This reaction offers an efficient, mild, and high-yielding method for the preparation of substituted α,β-unsaturated compounds