Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Direct observation of β-alkynyl eliminations from unstrained propargylic alkoxide Cu($$\tiny{I}$$) complexes by C–C bond cleavage

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/d4sc02982h· OSTI ID:2453927
 [1];  [1];  [1];  [1];  [1]
  1. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
+ Show Author Affiliations
β-Carbon eliminations of aryl, allylic, and propargylic alkoxides of Rh(I), Pd(II), and Cu(I) are key elementary reactions in the proposed mechanisms of homogeneously catalysed cross-coupling, group transfer, and annulation. Besides the handful of studies with isolable Rh(I)-alkoxides, β-carbon eliminations of Pd(II)- and Cu(I)-alkoxides are less definitive. Herein, we provide a comprehensive synthetic, structural, and mechanistic study on the β-alkynyl eliminations of isolable secondary and tertiary propargylic alkoxide Cu(I) complexes, LCuOC(H)(Ph)C[triple bond, length as m-dash]CPh and LCuOC(ArF)2C[triple bond, length as m-dash]CPh (L = N-heterocyclic carbene (NHC), dppf, S-BINAP), to produce monomeric (NHC)CuC[triple bond, length as m-dash]CPh, dimeric [(diphosphine)CuC[triple bond, length as m-dash]CPh]2, and the corresponding carbonyl. Selective β-alkynyl over β-hydrogen elimination was observed for NHC- and diphosphine-supported secondary propargylic alkoxide complexes. The mechanism for the first-order reaction of β-carbon elimination of (IPr*Me)CuOC(ArF)2C[triple bond, length as m-dash]CPh is proposed to occur through an organized four-centred transition state via a Cu-alkyne π complex based on Eyring analysis of variable-temperature reaction rates by UV-vis kinetic analysis to provide ΔH‡ = 24(1) kcal mol-1, ΔS‡ = -8(3) e.u., and ΔG‡ (25 °C) = 27 kcal mol-1 over a temperature range of 60–100 °C. Additional quantitative UV-vis kinetic studies conclude that the electronic and steric properties of the NHC ligands engendered a marginal effect on the elimination rate, requiring 2–3 h at 100 °C for completion, whereas complete β-alkynyl eliminations of diphosphine-supported propargylic alkoxides were observed in 1–2 h at 25 °C.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
AC02-05CH11231; AC05-76RL01830
OSTI ID:
2453927
Alternate ID(s):
OSTI ID: 2515632
Report Number(s):
PNNL-SA--198168
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 42 Vol. 15; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (41)

Rhodium‐Catalyzed Rearrangement of Aryl Bis(alkynyl) Carbinols to 3‐Alkynyl‐1‐indanones journal February 2008
Allyl‐, Allenyl‐, and Propargyl‐Transfer Reactions through Cleavage of CC Bonds Catalyzed by an N‐Heterocyclic Carbene/Copper Complex: Synthesis of Multisubstituted Pyrroles journal March 2011
Bis-NHC Chelate Complexes of Nickel(0) and Platinum(0) journal May 2014
Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity journal March 2020
Rhodium‐Catalyzed/Copper‐Mediated Selective C2 Alkynylation of Indoles and C1 Alkynylation of Carbazoles with γ‐Substituted tert‐Propargyl Alcohols journal May 2016
Rhenium-Promoted C−C Bond-Cleavage Reactions of Internal Propargyl Alcohols journal June 2018
Nonlinear d 10 -ML 2 Transition-Metal Complexes journal May 2013
Metal-Catalyzed Carbon–Carbon Bond Cleavage of Unstrained Alcohols journal July 2020
Introduction: Click Chemistry journal June 2021
β-Alkyl Elimination: Fundamental Principles and Some Applications journal June 2016
Collaboration as a Key to Advance Capabilities for Earth-Abundant Metal Catalysis journal March 2023
Structural Characterization of β-Agostic Bonds in Pd-Catalyzed Polymerization journal September 2017
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion journal October 2016
Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections journal November 2012
Copper Chalcogenide Clusters Stabilized with Ferrocene-Based Diphosphine Ligands journal May 2013
Metal-Alkyl Group Effects on the Thermodynamic Stability and Stereochemical Mobility of B(C 6 F 5 ) 3 -Derived Zr and Hf Metallocenium Ion-Pairs journal October 2000
Ethylene insertion and .beta.-hydrogen elimination for permethylscandocene alkyl complexes. A study of the chain propagation and termination steps in Ziegler-Natta polymerization of ethylene journal February 1990
[Bis(dicyclohexylphosphino)ethane]platinum(0). Reactions with alkyl, (trimethylsilyl)methyl, aryl, benzyl, and alkynyl carbon-hydrogen bonds journal March 1988
Choice of Coordination Number in d 10 Complexes of Group 11 Metals journal January 2004
Regio- and Stereoselective Homocoupling of γ-Arylated tert-Propargyl Alcohols with Liberation of a Ketone Molecule and Successive Cyclization To Produce Fluorescent Dihydrofuran Derivatives journal October 2005
Direct Observation of β-Aryl Eliminations from Rh(I) Alkoxides journal February 2006
Rhodium-Catalyzed Asymmetric Rearrangement of Alkynyl Alkenyl Carbinols:  Synthetic Equivalent to Asymmetric Conjugate Alkynylation of Enones journal October 2007
Copper-Catalyzed Enantioselective Propargylic Amination of Propargylic Esters with Amines: Copper−Allenylidene Complexes as Key Intermediates journal July 2010
A Highly Selective Synthesis of Diarylethynes and Their Oligomers by a Palladium-Catalyzed Sonogashira Coupling Reaction under Phase Transfer Conditions journal February 2001
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Palladium-Catalyzed Oxidative Alkynylation of Alkenes via C−C Bond Cleavage under Oxygen Atmosphere journal July 2003
Measurement of the Barrier to β-Hydride Elimination in a β-Agostic Palladium−Ethyl Complex:  A Model for the Energetics of Chain-Walking in (α-Diimine)PdR + Olefin Polymerization Catalysts journal September 2001
Copper(I) Alkyne and Alkynide Complexes journal August 2012
Insertions of Ketones and Nitriles into Organorhodium(I) Complexes and β-Hydrocarbyl Eliminations from Rhodium(I) Alkoxo and Iminyl Complexes journal August 2008
Novel Copper(I) Complexes Containing 1,1‘-Bis(diphenylphosphino)ferrocene (dppf) as a Chelate and Bridging Ligand:  Synthesis of Tetrabridged Dicopper(I) Complexes [Cu 2 (μ-η 1 -C⋮R) 2 (μ-dppf) 2 ] and X-ray Crystal Structure of [Cu 2 (μ-η 1 -C⋮CC 6 H 4 CH 3 -4) 2 (μ-dppf) 2 ] journal February 1999
Towards the online computer-aided design of catalytic pockets journal September 2019
Turning unreactive copper acetylides into remarkably powerful and mild alkyne transfer reagents by oxidative umpolung journal January 2014
Rh/Cu-catalyzed multiple C–H, C–C, and C–N bond cleavage: facile synthesis of pyrido[2,1-a]indoles from 1-(pyridin-2-yl)-1H-indoles and γ-substituted propargyl alcohols journal January 2015
Accelerating the insertion reactions of (NHC)Cu–H via remote ligand functionalization journal January 2021
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
Theoretical studies on β-aryl elimination from Rh(i) complexes journal January 2009
Copper-catalyzed azide–alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(i) acetylides journal January 2010
Synthesis, crystal structures and reactivity of copper(i) amidate complexes with aryl halides: insight into copper(i)-catalyzed Goldberg reaction journal January 2012
Cobalt-catalyzed asymmetric hydrogenation of enamides enabled by single-electron reduction journal May 2018
Using nature’s blueprint to expand catalysis with Earth-abundant metals journal August 2020
Cross-coupling by a noncanonical mechanism involving the addition of aryl halide to Cu(II) journal September 2023

Similar Records

Trends in Homolytic Bond Dissociation Energies of Five- and Six-Coordinate Hydrides of Group 9 Transition Metals: Co, Rh, Ir
Journal Article · Mon Jan 30 19:00:00 EST 2017 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1480250

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY