skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synergistic Bimetallic Ni/Ag and Ni/Cu Catalysis for Regioselective γ,δ-Diarylation of Alkenyl Ketimines: Addressing β-H Elimination by in Situ Generation of Cationic Ni(II) Catalysts

Abstract

Here, we disclose unprecedented synergistic bimetallic Ni/Ag and Ni/Cu catalysts for regioselective γ,δ-diarylation of unactivated alkenes in simple ketimines with aryl halides and arylzinc reagents. The bimetallic synergy, which generates cationic Ni(II) species during reaction, promotes migratory insertion and transmetalation steps and suppresses β-H elimination and cross-coupling, the major side reactions that cause serious problems during alkene difunctionalization. This diarylation reaction proceeds at remote locations to imines to afford, after simple H+ workup, diversely substituted γ,δ-diaryl ketones that are otherwise difficult to access readily with existing methods.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. The Univ. of New Mexico, Albuquerque, NM (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1485460
Report Number(s):
SAND-2018-12087J
Journal ID: ISSN 0002-7863; 668982
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 46; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Basnet, Prakash, KC, Shekhar, Dhungana, Roshan K., Shrestha, Bijay, Boyle, Timothy J., and Giri, Ramesh. Synergistic Bimetallic Ni/Ag and Ni/Cu Catalysis for Regioselective γ,δ-Diarylation of Alkenyl Ketimines: Addressing β-H Elimination by in Situ Generation of Cationic Ni(II) Catalysts. United States: N. p., 2018. Web. doi:10.1021/jacs.8b09401.
Basnet, Prakash, KC, Shekhar, Dhungana, Roshan K., Shrestha, Bijay, Boyle, Timothy J., & Giri, Ramesh. Synergistic Bimetallic Ni/Ag and Ni/Cu Catalysis for Regioselective γ,δ-Diarylation of Alkenyl Ketimines: Addressing β-H Elimination by in Situ Generation of Cationic Ni(II) Catalysts. United States. https://doi.org/10.1021/jacs.8b09401
Basnet, Prakash, KC, Shekhar, Dhungana, Roshan K., Shrestha, Bijay, Boyle, Timothy J., and Giri, Ramesh. 2018. "Synergistic Bimetallic Ni/Ag and Ni/Cu Catalysis for Regioselective γ,δ-Diarylation of Alkenyl Ketimines: Addressing β-H Elimination by in Situ Generation of Cationic Ni(II) Catalysts". United States. https://doi.org/10.1021/jacs.8b09401. https://www.osti.gov/servlets/purl/1485460.
@article{osti_1485460,
title = {Synergistic Bimetallic Ni/Ag and Ni/Cu Catalysis for Regioselective γ,δ-Diarylation of Alkenyl Ketimines: Addressing β-H Elimination by in Situ Generation of Cationic Ni(II) Catalysts},
author = {Basnet, Prakash and KC, Shekhar and Dhungana, Roshan K. and Shrestha, Bijay and Boyle, Timothy J. and Giri, Ramesh},
abstractNote = {Here, we disclose unprecedented synergistic bimetallic Ni/Ag and Ni/Cu catalysts for regioselective γ,δ-diarylation of unactivated alkenes in simple ketimines with aryl halides and arylzinc reagents. The bimetallic synergy, which generates cationic Ni(II) species during reaction, promotes migratory insertion and transmetalation steps and suppresses β-H elimination and cross-coupling, the major side reactions that cause serious problems during alkene difunctionalization. This diarylation reaction proceeds at remote locations to imines to afford, after simple H+ workup, diversely substituted γ,δ-diaryl ketones that are otherwise difficult to access readily with existing methods.},
doi = {10.1021/jacs.8b09401},
url = {https://www.osti.gov/biblio/1485460}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 46,
volume = 140,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Strategies toward Dicarbofunctionalization of Unactivated Olefins by Combined Heck Carbometalation and Cross-Coupling
journal, February 2018


Transition Metal-Catalyzed Dicarbofunctionalization of Unactivated Olefins
journal, March 2018


Iron-Catalyzed Olefin Carbometalation
journal, January 2000


Nickel-Catalyzed Reductive Dicarbofunctionalization of Alkenes
journal, May 2017


Regioselective Double Alkylation of Styrenes with Alkyl Halides Using a Titanocene Catalyst
journal, November 1998


Palladium-catalyzed iodine-zinc exchange reactions. A new palladium-mediated intramolecular carbozincation of alkenes
journal, July 1993


Cobalt-Catalyzed Tandem Radical Cyclization and Cross-Coupling Reaction:  Its Application to Benzyl-Substituted Heterocycles
journal, June 2001


Ni-Catalyzed Cascade Formation of C(sp3)C(sp3) Bonds by Cyclization and Cross-Coupling Reactions of Iodoalkanes with Alkyl Zinc Halides
journal, November 2007


Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles
journal, February 2014


Diarylation of Alkenes by a Cu-Catalyzed Migratory Insertion/Cross-Coupling Cascade
journal, October 2014


Catalytic Enantioselective Diarylation of Alkenes
journal, November 2015


Manganese-Catalyzed Carboacylations of Alkenes with Alkyl Iodides
journal, August 2016


Pd-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Unactivated Olefins by a Heck Reaction/Enolate Cyclization Cascade
journal, April 2017


Copper-Catalyzed Dicarbofunctionalization of Unactivated Olefins by Tandem Cyclization/Cross-Coupling
journal, April 2017


Ni-Catalyzed Alkene Carboacylation via Amide C–N Bond Activation
journal, July 2017


Stereoselective synthesis of a Podophyllum lignan core by intramolecular reductive nickel-catalysis
journal, January 2018


Ni-catalyzed two-component reductive dicarbofunctionalization of alkenes via radical cyclization
journal, January 2018


Catalytic conjunctive cross-coupling enabled by metal-induced metallate rearrangement
journal, December 2015


Palladium-Catalyzed Oxidative Intermolecular Difunctionalization of Terminal Alkenes with Organostannanes and Molecular Oxygen
journal, April 2009


Ni-Catalyzed Regioselective Alkylarylation of Vinylarenes via C(sp 3 )–C(sp 3 )/C(sp 3 )–C(sp 2 ) Bond Formation and Mechanistic Studies
journal, July 2018


Nickel-Catalyzed Stereoselective Diarylation of Alkenylarenes
journal, July 2018


Asymmetric Cu-Catalyzed Intermolecular Trifluoromethylarylation of Styrenes: Enantioselective Arylation of Benzylic Radicals
journal, February 2017


Copper-Mediated Cyanotrifluoromethylation of Styrenes Using the Togni Reagent
journal, October 2013


Copper-Catalyzed Intermolecular Cyanotrifluoromethylation of Alkenes
journal, December 2013


Enantioselective Copper-Catalyzed Intermolecular Cyanotrifluoromethylation of Alkenes via Radical Process
journal, November 2016


Enantioselective Trifluoromethylalkynylation of Alkenes via Copper-Catalyzed Radical Relay
journal, August 2018


Copper-Catalyzed Intermolecular Trifluoromethylarylation of Alkenes: Mutual Activation of Arylboronic Acid and CF 3 + Reagent
journal, July 2014


A Palladium-Catalyzed Three-Component Cross-Coupling of Conjugated Dienes or Terminal Alkenes with Vinyl Triflates and Boronic Acids
journal, April 2011


Enantioselective 1,2-Difunctionalization of Dienes Enabled by Chiral Palladium Complex-Catalyzed Cascade Arylation/Allylic Alkylation Reaction
journal, October 2015


Nickel-Catalyzed Regioselective Three Component Coupling Reaction of Alkyl Halides, Butadienes, and Ar-M (M=MgX, ZnX)
journal, July 2004


Cobalt-Catalyzed Three-Component Coupling Reaction of Alkyl Halides, 1,3-Dienes, and Trimethylsilylmethylmagnesium Chloride
journal, October 2003


Palladium-Catalyzed 1,4-Difunctionalization of Butadiene To Form Skipped Polyenes
journal, March 2013


Nickel-Catalyzed Heck-Type Reactions of Benzyl Chlorides and Simple Olefins
journal, November 2011


Enantiospecific Intramolecular Heck Reactions of Secondary Benzylic Ethers
journal, May 2014


Mild and Efficient Nickel-Catalyzed Heck Reactions with Electron-Rich Olefins
journal, December 2011


Construction of Quaternary Stereocenters by Nickel-Catalyzed Heck Cyclization Reactions
journal, September 2016


Nickel-Catalyzed Reductive Conjugate Addition of Primary Alkyl Bromides to Enones To Form Silyl Enol Ethers
journal, January 2017


Palladium-Catalyzed 1,1-Difunctionalization of Ethylene
journal, July 2012


Pd II -Catalyzed Oxidative 1,1-Diarylation of Terminal Olefins
journal, May 2010


Pd(0)-Catalyzed 1,1-Diarylation of Ethylene and Allylic Carbonates
journal, September 2013


Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles
journal, July 2017


Tandem Difluoroalkylation-Arylation of Enamides Catalyzed by Nickel
journal, September 2016


Nickel-Catalyzed β,γ-Dicarbofunctionalization of Alkenyl Carbonyl Compounds via Conjunctive Cross-Coupling
journal, July 2017


Directed nickel-catalyzed 1,2-dialkylation of alkenyl carbonyl compounds
journal, January 2018


Thermal decomposition of bis(phosphine)platinum(II) metallocycles
journal, October 1976


Asymmetric Heck Reactions via Neutral Intermediates: Enhanced Enantioselectivity with Halide Additives Gives Mechanistic Insights
journal, March 1997


1,10-Phenanthroline derivatives: a new ligand class in the Heck reaction. Mechanistic aspects
journal, December 1993


“Cationic” Suzuki–Miyaura Coupling with Acutely Base-Sensitive Boronic Acids
journal, September 2017


On the Nature of the "Copper Effect" in the Stille Cross-Coupling
journal, October 1994


Stille Coupling Made Easier—The Synergic Effect of Copper(I) Salts and the Fluoride Ion
journal, February 2004


Stereospecific Palladium‐Catalyzed Acylation of Enantioenriched Alkylcarbastannatranes: A General Alternative to Asymmetric Enolate Reactions
journal, December 2016


A new, easy synthesis of phenylsilver
journal, January 1977


Reaction of diarylzinc compounds with copper(I) salts. Synthesis and characterization of arylcopper(I) compounds
journal, January 1978


Works referencing / citing this record:

Nickel-Catalyzed Asymmetric Reductive Diarylation of Vinylarenes
journal, February 2019


Three-component vicinal-diarylation of alkenes via direct transmetalation of arylboronic acids
journal, January 2019


Nickel‐Catalyzed 1,2‐Diarylation of Alkenyl Carboxylates: A Gateway to 1,2,3‐Trifunctionalized Building Blocks
journal, December 2019


Nickel‐Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes
journal, April 2019


Palladium‐Catalyzed Directed meta ‐Selective C−H Allylation of Arenes: Unactivated Internal Olefins as Allyl Surrogates
journal, June 2019


Cu-Catalyzed cyanoalkylation of electron-deficient alkenes with unactivated alkyl bromides
journal, January 2019


Facile Preparation of Spirolactones by an Alkoxycarbonyl Radical Cyclization–Cross‐Coupling Cascade
journal, May 2019


Synthesis of All‐Carbon Quaternary Centers by Palladium‐Catalyzed Olefin Dicarbofunctionalization
journal, February 2020


Synthese quartärer Kohlenstoffzentren durch palladiumkatalysierte Dicarbofunktionalisierung
journal, December 2019


Coordination Assisted Distal C−H Alkylation of Fused Heterocycles
journal, August 2019


Introduction of Ag/CuO/MCM‐48 as an efficient catalyst for the one‐pot synthesis of novel pyran‐pyrrole hybrids
journal, July 2019


Nickel-catalyzed intermolecular oxidative Heck arylation driven by transfer hydrogenation
journal, November 2019


Coordination Assisted Distal C−H Alkylation of Fused Heterocycles
journal, July 2019


Nickel‐Catalyzed 1,2‐Diarylation of Alkenyl Carboxylates: A Gateway to 1,2,3‐Trifunctionalized Building Blocks
journal, December 2019


Nickel‐Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes
journal, May 2019


Nickel‐Catalyzed Asymmetric Reductive Diarylation of Vinylarenes
journal, January 2019


Enantioselective Radical Addition/Cross‐Coupling of Organozinc Reagents, Alkyl Iodides, and Alkenyl Boron Reagents
journal, August 2019


Enantioselective Radical Addition/Cross‐Coupling of Organozinc Reagents, Alkyl Iodides, and Alkenyl Boron Reagents
journal, August 2019


Facile Preparation of Spirolactones by an Alkoxycarbonyl Radical Cyclization–Cross‐Coupling Cascade
journal, June 2019


Direct Carbohydroxylation of Arylalkenes with Allylic Alcohols: Cooperative Catalysis of Copper, Silver, and a Brønsted Acid
journal, February 2019


Palladium‐Catalyzed Directed meta ‐Selective C−H Allylation of Arenes: Unactivated Internal Olefins as Allyl Surrogates
journal, July 2019