Palladium-Catalyzed, Asymmetric Mizoroki–Heck Reaction of Benzylic Electrophiles Using Phosphoramidites as Chiral Ligands

We report herein the first examples of asymmetric Mizoroki–Heck reactions using benzyl electrophiles. A new phosphoramidite was identified to be an effective chiral ligand in the palladium–catalyzed reaction. The reaction is compatible with polar functional groups and can be readily scaled up. Several cyclic olefins worked well as olefin components. Thirty-one examples are included

<i>N</i>,<i>N</i>‑Dimethylformamide as Hydride Source in Nickel-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated Esters

Asymmetric transfer hydrogenation of α,β-unsaturated esters is realized by using a nickel/bisphosphine catalyst and <i>N</i>,<i>N</i>-dimethylformamide (DMF) as the hydride source

Palladium-Catalyzed, Asymmetric Mizoroki–Heck Reaction of Benzylic Electrophiles Using Phosphoramidites as Chiral Ligands

We report herein the first examples of asymmetric Mizoroki–Heck reactions using benzyl electrophiles. A new phosphoramidite was identified to be an effective chiral ligand in the palladium–catalyzed reaction. The reaction is compatible with polar functional groups and can be readily scaled up. Several cyclic olefins worked well as olefin components. Thirty-one examples are included

Palladium-Catalyzed Alkynylation and Concomitant <i>ortho</i> Alkylation of Aryl Iodides

We report an efficient alkynylation reaction of aryl iodides with simultaneous <i>ortho</i>-alkylaton of aryl rings. The reaction between three simple reagentsaryl halides, alkynes, and alkyl halidesformed aryl–alkynyl bonds carrying hindered aryl rings in one step. The reaction proceeded via a Catellani-type pathway in the presence of norbornene. From a synthetic perspective, this reaction allows quick access toward many 1,2,3-substituted arenes and multiply substituted benzofurans, after manipulation of alkyne groups. These compounds are difficult to synthesize otherwise

Palladium-Catalyzed Alkynylation and Concomitant <i>ortho</i> Alkylation of Aryl Iodides

We report an efficient alkynylation reaction of aryl iodides with simultaneous <i>ortho</i>-alkylaton of aryl rings. The reaction between three simple reagentsaryl halides, alkynes, and alkyl halidesformed aryl–alkynyl bonds carrying hindered aryl rings in one step. The reaction proceeded via a Catellani-type pathway in the presence of norbornene. From a synthetic perspective, this reaction allows quick access toward many 1,2,3-substituted arenes and multiply substituted benzofurans, after manipulation of alkyne groups. These compounds are difficult to synthesize otherwise

Palladium-Catalyzed Arylation of Ketones and Acetonitrile with <i>Ortho</i> Alkylation of Aryl Rings: De Novo Synthesis of Tetralines and Benzocycloheptenes

Palladium-catalyzed α-arylation reactions of ketones with simultaneous <i>ortho</i> alkylation offer 1,2,3-substituted arenes. The reactions of 1,ω-dihaloalkanes also allow facile construction of medicinally important tetralines and benzocycloheptenes

Palladium-Catalyzed Arylation of Ketones and Acetonitrile with <i>Ortho</i> Alkylation of Aryl Rings: De Novo Synthesis of Tetralines and Benzocycloheptenes

Palladium-catalyzed α-arylation reactions of ketones with simultaneous <i>ortho</i> alkylation offer 1,2,3-substituted arenes. The reactions of 1,ω-dihaloalkanes also allow facile construction of medicinally important tetralines and benzocycloheptenes

Iridium-Catalyzed, Intermolecular Hydroamination of Unactivated Alkenes with Indoles

The addition of an N–H bond to an olefin is the most direct route for the synthesis of alkylamines. Currently, intermolecular hydroamination is limited to reactions of a narrow range of reagents containing N–H bonds or activated alkenes, and all the examples of additions to unactivated alkenes require large excesses of alkene. We report intermolecular hydroamination reactions of indoles with unactivated olefins. The reactions occur with as few as 1.5 equiv of olefin to form <i>N</i>-alkylindoles exclusively and in good yield. Characterizations of the catalyst resting state, kinetic data, labeling studies, and computational data imply that the addition occurs by olefin insertion into the Ir–N bond of an <i>N</i>-indolyl complex and that this insertion reaction is faster than insertion of olefin into the Ir–C bond of the isomeric C-2-indolyl complex

Iridium-Catalyzed Intermolecular Hydroamination of Unactivated Aliphatic Alkenes with Amides and Sulfonamides

The intermolecular addition of N–H bonds to unactivated alkenes remains a challenging, but desirable, strategy for the synthesis of <i>N</i>-alkylamines. We report the intermolecular amination of unactivated α-olefins and bicycloalkenes with arylamides and sulfonamides to generate synthetically useful protected amine products in high yield. Mechanistic studies on this rare catalytic reaction revealed a resting state that is the product of N–H bond oxidative addition and coordination of the amide. Rapid, reversible dissociation of the amide precedes reaction with the alkene, but an intramolecular, kinetically significant rearrangement of the species occurs before this reaction with alkene

Iridium-Catalyzed Intermolecular Hydroamination of Unactivated Aliphatic Alkenes with Amides and Sulfonamides

The intermolecular addition of N–H bonds to unactivated alkenes remains a challenging, but desirable, strategy for the synthesis of <i>N</i>-alkylamines. We report the intermolecular amination of unactivated α-olefins and bicycloalkenes with arylamides and sulfonamides to generate synthetically useful protected amine products in high yield. Mechanistic studies on this rare catalytic reaction revealed a resting state that is the product of N–H bond oxidative addition and coordination of the amide. Rapid, reversible dissociation of the amide precedes reaction with the alkene, but an intramolecular, kinetically significant rearrangement of the species occurs before this reaction with alkene