Ni-Catalyzed Regioselective Alkenylarylation of γ,δ-Alkenyl Ketones via Carbonyl Coordination.

  title={Ni-Catalyzed Regioselective Alkenylarylation of $\gamma$,$\delta$-Alkenyl Ketones via Carbonyl Coordination.},
  author={Roshan K. Dhungana and Vivek Aryal and Doleshwar Niroula and Rishi R Sapkota and Margaret G. Lakomy and Ramesh Giri},
  journal={Angewandte Chemie},
We disclose a nickel-catalyzed reaction, which enabled us to difunctionalize unactivated γ,δ-alkenes in ketones with alkenyl triflates and arylboronic esters. The reaction was made feasible by the use of 5-chloro-8-hydroxyquinoline as a ligand along with NiBr 2 •DME as a catalyst and LiO t Bu as base. The reaction proceeded with a wide range of cyclic, acyclic, endocyclic and exocyclic alkenyl ketones, and electron-rich and electron-deficient arylboronate esters. The reaction also worked with… 
3 Citations
Nickel-Catalyzed Regio- and Enantioselective Hydroamination of Unactivated Alkenes Using Carbonyl Directing Groups.
The asymmetric addition of an N-H bond to various alkenes via a direct catalytic method is a powerful way of synthesizing value-added chiral amines. Therefore, the enantio- and regioselective
Electrophilic Sulfur Reagent Design Enables Directed syn-Carbosulfenylation of Unactivated Alkenes.
A multi-component approach to structurally complex organosulfur products is described via the nickel-catalyzed 1,2-carbosulfenylation of unactivated alkenes with organoboron nucleophiles and tailored


Nickel-Catalyzed β,γ-Dicarbofunctionalization of Alkenyl Carbonyl Compounds via Conjunctive Cross-Coupling.
The methodology developed herein represents the first three-component 1,2-dicarbofunctionalization of non-conjugated alkenes involving a C(sp3)-C( sp3) reductive elimination step.
Nickel-Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes.
Preliminary mechanistic investigations reveal that this Ni-catalyzed reaction proceeds as a cascade consisting of migratory insertion and cross-coupling with a nickel(I)-mediated intramolecular 5-exo cyclization as the enantiodetermining step.
Nickel-Catalyzed 1,2-Diarylation of Simple Alkenyl Amides.
This method represents the first example of regiocontrolled 1,2-diarylation directed by a native amide functional group and sheds light on the potential substrate binding mode and the role of the EDO ligand in the reductive elimination step.
Nickel-Catalyzed Dicarbofunctionalization of Alkenes.
Great opportunities exist for the development of three-component difunctionalization reactions with broad substrate scopes and tunable chemo-, regio-, and stereoselectivities.
Ni-Catalyzed Regioselective β,δ-Diarylation of Unactivated Olefins in Ketimines via Ligand-Enabled Contraction of Transient Nickellacycles: Rapid Access to Remotely Diarylated Ketones.
This diarylation proceeds at remote locations to the carbonyl group to afford, after simple H+ workup, diversely substituted β,δ-diarylketones that are otherwise difficult to access readily with existing methods.
Pd-Catalyzed Alkene Difunctionalization Reactions of Enolates for the Synthesis of Substituted Bicyclic Cyclopentanes.
Palladium-catalyzed alkene difunctionalization reactions between alkenes bearing tethered aryl or alkenyl triflates and enolate nucleophiles are described, producing substituted cyclopentane derivatives that contain appended carbonyl functionality.
Pd-Catalyzed Alkene Difunctionalization Reactions of Malonate Nucleophiles: Synthesis of Substituted Cyclopentanes via Alkene Aryl-Alkylation and Akenyl-Alkylation.
The Pd-catalyzed coupling of malonate nucleophiles with alkenes bearing tethered aryl or alkenyl triflates is described, and the transformations generate a five-membered ring, two C-C bonds, and provide products bearing up to three stereocenters with good chemical yield and generally high diastereoselectivity.
Nickel-Catalyzed 1,2-Diarylation of Alkenyl Carboxylates: A Gateway to 1,2,3-Trifunctionalized Building Blocks.
This method represents the first example of catalytic 1,2-diarylation of an alkene directed by a native carboxylate group and improves three routes toward bioactive molecules in terms of yield and/or step count.
Stereoselective and Regioselective Synthesis of Heterocycles via Copper-Catalyzed Additions of Amine Derivatives and Alcohols to Alkenes.
This Perspective describes the development of a family of copper(II)-catalyzed alkene difunctionalization reactions that enable stereoselective addition of amine derivatives and alcohols onto pendant
Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles.
This approach utilizes a readily removable imine as a coordinating group that plays a dual role of intercepting oxidative addition species derived from aryl halides and triflates to promote Heck carbometalation and stabilizing the Heck C(sp3)-NiX intermediates as transient metallacycles to suppress β-hydride elimination and facilitate transmetalation/reductive elimination steps.