CpRuII-chiral bisamidine complex catalyzed asymmetric Carroll-type decarboxylative allylation of β-keto allyl esters

Asymmetric Dehydrative Allylation Using Soft Ruthenium and Hard Brønsted Acid Combined Catalyst

“…A well‐defined chiral environment can be constructed by the two dioxolane rings, which can protrude up and down on the core Naph‐diPIM plane owing to the [3.3.0] ring system. The utilization of the ligand has been realized in a series of reactions including Ru(II)‐catalyzed Carroll‐type decarboxylative allylation, [24] Cu(II)‐catalyzed Friedel‐Crafts reaction of indoles, [25] Zn(II)‐catalyzed Diels‐Alder reaction, [26] Zn(II)‐catalyzed 1,3‐dipolar cycloaddition, [27] Co‐catalyzed NaBH 4 reduction of α,β‐unsaturated carboxylic esters, [28] and Cu(I)‐catalyzed oxidative coupling of 1,3‐dicarbonyl compounds with simple alkenes [29] …”

“…A well-defined chiral environment can be constructed by the two dioxolane rings, which can protrude up and down on the core Naph-diPIM plane owing to the [3.3.0] ring system. The utilization of the ligand has been realized in a series of reactions including Ru(II)-catalyzed Carroll-type decarboxylative allylation, [24] Cu-(II)-catalyzed Friedel-Crafts reaction of indoles, [25] Zn(II)catalyzed Diels-Alder reaction, [26] Zn(II)-catalyzed 1,3-dipolar cycloaddition, [27] Co-catalyzed NaBH 4 reduction of α,β-unsaturated carboxylic esters, [28] and Cu(I)-catalyzed oxidative coupling of 1,3-dicarbonyl compounds with simple alkenes. [29] In the monocationic CpRu(II) complex combined with a Brønsted acid, for example [Ru(II)Cp(Naph-diPIM-dioxo-iPr)]PF 6 (26)/p-TsOH, the central Ru(II) is expected to show high nucleophilicity because of the strong connection between the highly electron-donating Naph-diPIM-dioxo-R and monoanionic Cp ligands.…”

The Allylic Alkylation of Ketone Enolates

“…Recently, a new ligand for the Ru catalyzed decarboxylative allylic alkylation was introduced, which provided even better enantioselectivities. Kitamura and coworkers reported, that a Ru‐complex formed from CpRu and chiral bisamidine L9 provided nearly perfect enantioselectivity in the Ru‐catalyzed rearrangement of cinnamyl acetoacetates (Scheme ) . Remarkably, the reaction could be performed with 0.1 mol % of catalyst, which resulted in prolonged reaction times of 48 h (compared to 6 h with 1 mol % catalyst), but the products could still be obtained in high yields and enantiomeric excesses.…”