Ruthenium-Catalyzed Cross-Coupling Research Articles

Ruthenium-Catalyzed Cross-Coupling of Ketones as an Alkenyl Electrophile with Organoborons via Cleavage of Alkenyl C-N Bonds of in Situ Generated Enamines.

A ruthenium-catalyzed cross-coupling reaction of ketones with organoboronic esters was developed. In this reaction, ketones possessing a pyridine-directing group directly functions as an alkenyl electrophile for coupling with organoboronates in the presence of pyrrolidine and a ruthenium catalyst. This reaction proceeds via the catalytic cleavage of the alkenyl carbon-nitrogen bond in the enamines generated in situ from ketones with pyrrolidine, benzylamine, or isoindoline.

Ruthenium-Catalyzed Cross-Coupling of Anilines

Ruthenium-Catalyzed Cross-Coupling of Anilines

Ruthenium-Catalyzed Cross-Coupling of Maleimides with Alkenes.

The cross-coupling of maleimides with electron-deficient alkenes such as acrylates proceeds smoothly under ruthenium catalysis. This unique C-C coupling provides a simple, straightforward synthetic method for preparing alkylidene succinimide derivatives.

Ruthenium-Catalyzed Cross-Coupling of Naphthamides

Key words ruthenium - ortho metalation - naphthamides - aryl boronates

Beyond Directed ortho Metalation: Ruthenium-Catalyzed Amide-Directed CAr–OMe Activation/Cross-Coupling Reaction of Naphthamides with Aryl Boronates

A new and general synthetic methodology for the construction of biaryl, heterobiaryl, and polyaryl molecules by the ruthenium-catalyzed cross-coupling of ortho-methoxy naphthamides with aryl boroneopentylates is described. The isomeric 1-MeO-2-naphthamides and 2-MeO-1-naphthamides furnish an expansive series of arylated naphthamides in excellent yields. Competition experiments showed the higher reactivity of 1-MeO-2-naphthamide over 2-MeO-benzamide. Orthogonality between the C-O activation/cross-coupling and the Suzuki-Miyaura reactions was established. The method provides naphthalenes which are difficult to prepare by directed ortho metalation.

Synthesis of arylketones by ruthenium-catalyzed cross-coupling of aldehydes with arylboronic acids

The first ruthenium-catalyzed cross-coupling of aldehydes with arylboronic acids is reported. Various aliphatic and aromatic aldehydes are transformed to the corresponding arylketones. A total of 31 examples with moderate to excellent yields are presented, together with the results of an initial mechanistic investigation.

Ruthenium-Catalyzed Cross-Coupling of Tertiary Propargyl Alcohols with ω-Alkynenitriles: A Regio- and Stereoselective Surrogate for an Aldol Condensation

A novel catalytic alkyne cross-coupling reaction is reported which connects tertiary propargyl alcohols with omega-alkynylnitriles with perfect atom economy. This remarkable process generates highly functionalized, stereodefined dienones that are formal aldol products in a single step. Moreover, the specificity of the cyano substituent for this reaction demonstrates the unique and somewhat underappreciated properties of that functional group.

Synthesis of Exo-enynes by Ruthenium-Catalyzed Cross Coupling Reaction of Hydroxy Allenes and 1-Alkynes

RuH2(PPh3)4 and ferrocenylphosphines catalyze cross coupling reaction of hydroxy allenes and 1-alkynes giving exo-enynes selectively.