A Cascade Dehydrogenative Cross-Coupling/Annulation Reaction of Benzamides with β‑Keto Esters for the Synthesis of Isoquinolinone Derivatives

A novel cascade DCC/annulation reaction of <i>N</i>-alkoxybenzamides with β-keto esters has been developed for the synthesis of isoquinolinone derivatives under palladium catalysis. A plausible mechanism involving α-C­(sp²)–H activation and a Pd­(II)/Pd­(IV) catalytic cycle is also proposed

Dehydrogenative Cross-Coupling Reaction between <i>N</i>‑Aryl α‑Amino Acid Esters and Phenols or Phenol Derivative for Synthesis of α‑Aryl α‑Amino Acid Esters

A novel dehydrogenative cross-coupling (DCC) reaction between <i>N</i>-arylglycine esters and phenols or 1,3,5-trimethoxybenzene was developed by copper catalysis using di<i>-tert</i>-butyl peroxide (DTBP) as an oxidant. Under optimized conditions, a range of <i>N</i>-arylglycine esters <b>1</b> underwent the DCC reaction smoothly with various phenols <b>2</b> or 1,3,5-trimethoxybenzene <b>4</b> to give desired α-aryl α -amino acid esters <b>3</b> or <b>5</b>, respectively, with high <i>ortho</i> regioselectivities in a moderate to excellent yield. A possible mechanism involving aromatic electrophilic substitution is proposed

Dehydrogenative Cross-Coupling Reaction by Cooperative Transition-Metal and Brønsted Acid Catalysis for the Synthesis of β‑Quinolinyl α‑Amino Acid Esters

A novel dehydrogenative cross-coupling (DCC) reaction between methylquinoline derivatives and <i>N</i>-aryl glycine esters was developed by a cooperative catalysis of copper salt and Brønsted acid, affording an efficient synthesis of β-quinolinyl α-amino acid esters. A plausible mechanism using a proton to activate the methylquinoline derivative and copper­(II) to activate <i>N</i>-aryl glycine ester has been proposed

A Four-Component Cascade C–H Functionalization/Cyclization/Nucleophilic Substitution Reaction To Construct α‑Functionalized Tetrahydro­quinolines by the Strategy of <i>in Situ</i> Directing Group Formation

A four-component cascade C–H functionalization/cyclization/nucleophilic substitution reactions of anilines, carboxylic anhydrides, propenol, and alkohols have been developed by a strategy of <i>in situ</i> directing group formation, affording an efficient and convenient synthesis of α-alkoxyl tetrahydro­quinolines from basic starting materials. A plausible mechanism involving rhodium­(III) catalytic C–H functionalization and double nucleophilic attacks is proposed. The nucleophilicity order of some alcohols is also obtained for the cascade reaction

Morita–Baylis–Hillman Reaction of α,β-Unsaturated Ketones with Allylic Acetates by the Combination of Transition-Metal Catalysis and Organomediation

An intermolecular Morita–Baylis–Hillman (MBH) reaction of α,β-unsaturated ketones with allylic acetates under the catalysis of 10 mol % of tetrakis­(triphenylphosphine)­palladium(0) and mediation of tributylphosphine has been developed in the presence of acetic acid, affording the desired α-coupling products. The MBH reaction has the advantages of good tolerance to many functional groups, excellent regioselectivity and <i>E</i>-stereoselectivity, and moderate to good yields

Transesterification for Synthesis of Carboxylates Using Aldehydes as Acyl Donors via C–H and C–O Bond Activations

A new type of transesterification between aryl, heteroaryl, alkyl <i>N</i>-heteroarene-2-carboxylates and various aldehydes by C–H and C–O bond activations has been developed for the synthesis of versatile carboxylates. A possible mechanism containing oxidative addition of acyl–O bond in parent ester and radical cleavage of sp² C–H bond in aldehyde is proposed

Cascade C–H Functionalization/Amidation Reaction for Synthesis of Azepinone Derivatives

A cascade C–H functionalization/amidation reaction of aminobiaryls with diazomalonates has been developed under rhodium catalysis, affording new azepinone derivatives in moderate to excellent yields

Domino Reactions Containing Different Types of Heck Reactions for Selective 3,3- and 1,3-Diarylations of Propenol with Aryl Halides by Triple Catalysis

A new domino Heck-isomerization/Saegusa/Heck reaction of propenol with aryl iodides has been developed for the synthesis of 3,3-diaryl propenals by triple transition-metal catalysis. Moreover, we also developed the domino Heck-isomerization/Heck-type reaction of propenol with aryl iodides for the synthesis of 1,3-diaryl propanones by double transition-metal catalysis and the mediation of secondary amine or triple transition metal catalysis and aminocatalysis

Coupling Reactions of Heteroarenes with Phosphites under Silver Catalysis

A silver-catalyzed dehydrogenative cross-coupling reaction of substituted furans, thiophene, thioazole, and pyrrole <b>1a</b>–<b>e</b> with dialkyl phosphites <b>2</b> was first developed to afford corresponding phosphonated products <b>3a</b>–<b>h</b> with up to 89% yield and good regioselectivities. Moreover, an unprecedented coupling of various substituted pyridines <b>1f</b>–<b>k</b> with dialkyl phosphites <b>2</b> using AgNO₃ as a catalyst and K₂S₂O₈ as an oxidant, followed by reduction with Na₂S₂O₃, was also realized to furnish desired pyridine phosphonates <b>3i</b>–<b>q</b> in satisfactory yields with good regioselectivities