Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity

Tran, Ba L.; Neisen, Benjamin D.; Speelman, Amy L.; Gunasekara, Thilina; Wiedner, Eric S.; Bullock, R. Morris

doi:10.1002/ange.201916406

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity

Journal Article · Fri Mar 20 04:00:00 EDT 2020 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201916406· OSTI ID:1633671

Tran, Ba L. ^[1]; Neisen, Benjamin D. ^[1]; ^[1]; ^[1]; ^[1]; ^[1]

Institute for Integrated Catalysis Pacific Northwest National Laboratory Richland WA 99352 USA

Abstract

We report mechanistic studies on the insertion reactions of [(NHC)Cu(μ‐H)] ₂ complexes with carbonyl substrates by UV‐vis and ¹ H NMR spectroscopic kinetic studies, H/D isotopic labelling, and X‐ray crystallography. The results of these comprehensive studies show that the insertion of Cu‐H with an aldehyde, ketone, activated ester/amide, and unactivated amide consist of two different rate limiting steps: the formation of Cu‐H monomer from Cu‐H dimer for more electrophilic substrates, and hydride transfer from a transient Cu‐H monomer for less electrophilic substrates. We also report spectroscopic and crystallographic characterization of rare Cu‐hemiacetalate and Cu‐hemiaminalate moieties from the insertion of an ester or amide into the Cu−H bond.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

OSTI ID:: 1633671

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 22 Vol. 132; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (99)

Hydrogenation of Carbon Dioxide to Formate Catalyzed by a Copper/1,8-Diazabicyclo[5.4.0]undec-7-ene System Watari, Ryo; Kayaki, Yoshihito; Hirano, Shin-ichi Advanced Synthesis & Catalysis, Vol. 357, Issue 7 https://doi.org/10.1002/adsc.201500043	journal	April 2015
Copper(I)-Catalyzed Asymmetric Hydrosilylations of Imines at Ambient Temperatures Lipshutz, Bruce H.; Shimizu, Hideo Angewandte Chemie, Vol. 116, Issue 17 https://doi.org/10.1002/ange.200353294	journal	April 2004
Vom Schleifen eines “Rohdiamanten”: die “Cu-H”-Katalyse mit Silanen Rendler, Sebastian; Oestreich, Martin Angewandte Chemie, Vol. 119, Issue 4 https://doi.org/10.1002/ange.200602668	journal	January 2007
Addition of Dimethylaminobismuth to Aldehydes, Ketones, Alkenes, and Alkynes Nekoueishahraki, Bijan; Sarish, Sankaranarayana Pillai; Roesky, Herbert W. Angewandte Chemie, Vol. 121, Issue 25 https://doi.org/10.1002/ange.200901215	journal	June 2009
Selective Reduction of Esters to Aldehydes under the Catalysis of Well-Defined NHC-Iron Complexes Li, Haoquan; Misal Castro, Luis C.; Zheng, Jianxia Angewandte Chemie, Vol. 125, Issue 31 https://doi.org/10.1002/ange.201303003	journal	June 2013
Chinese Puzzle Molecule: A 15 Hydride, 28 Copper Atom Nanoball Edwards, Alison J.; Dhayal, Rajendra S.; Liao, Ping‐Kuei Angewandte Chemie, Vol. 126, Issue 28 https://doi.org/10.1002/ange.201403324	journal	May 2014
Kupferhydrid-katalysierte Hydroaminierung von Alkenen und Alkinen Pirnot, Michael T.; Wang, Yi-Ming; Buchwald, Stephen L. Angewandte Chemie, Vol. 128, Issue 1 https://doi.org/10.1002/ange.201507594	journal	December 2015
Experimental and Computational Studies of the Copper Borate Complexes [(NHC)Cu(HBEt ₃ )] and [(NHC)Cu(HB(C ₆ F ₅ ) ₃ )] Collins, Lee R.; Rajabi, Nasir A.; Macgregor, Stuart A. Angewandte Chemie, Vol. 128, Issue 50 https://doi.org/10.1002/ange.201608081	journal	November 2016
Spectroscopic Evidence for a Monomeric Copper(I) Hydride and Crystallographic Characterization of a Monomeric Silver(I) Hydride Romero, Erik A.; Olsen, Pauline M.; Jazzar, Rodolphe Angewandte Chemie, Vol. 129, Issue 14 https://doi.org/10.1002/ange.201700858	journal	March 2017
Ein maskiertes Kupferhydrid als Katalysator für die Carbonylhydrosilylierung in wässrigen Lösungen Ritter, Florian; Mukherjee, Debabrata; Spaniol, Thomas P. Angewandte Chemie, Vol. 131, Issue 6 https://doi.org/10.1002/ange.201811890	journal	December 2018
Copper(I)-Catalyzed Asymmetric Hydrosilylations of Imines at Ambient Temperatures Lipshutz, Bruce H.; Shimizu, Hideo Angewandte Chemie International Edition, Vol. 43, Issue 17 https://doi.org/10.1002/anie.200353294	journal	April 2004
Polishing a Diamond in the Rough: “CuH” Catalysis with Silanes Rendler, Sebastian; Oestreich, Martin Angewandte Chemie International Edition, Vol. 46, Issue 4 https://doi.org/10.1002/anie.200602668	journal	January 2007
Addition of Dimethylaminobismuth to Aldehydes, Ketones, Alkenes, and Alkynes Nekoueishahraki, Bijan; Sarish, Sankaranarayana Pillai; Roesky, Herbert W. Angewandte Chemie International Edition, Vol. 48, Issue 25 https://doi.org/10.1002/anie.200901215	journal	June 2009
Selective Reduction of Esters to Aldehydes under the Catalysis of Well-Defined NHC-Iron Complexes Li, Haoquan; Misal Castro, Luis C.; Zheng, Jianxia Angewandte Chemie International Edition, Vol. 52, Issue 31 https://doi.org/10.1002/anie.201303003	journal	June 2013
Chinese Puzzle Molecule: A 15 Hydride, 28 Copper Atom Nanoball Edwards, Alison J.; Dhayal, Rajendra S.; Liao, Ping-Kuei Angewandte Chemie International Edition, Vol. 53, Issue 28 https://doi.org/10.1002/anie.201403324	journal	May 2014
Copper Hydride Catalyzed Hydroamination of Alkenes and Alkynes Pirnot, Michael T.; Wang, Yi-Ming; Buchwald, Stephen L. Angewandte Chemie International Edition, Vol. 55, Issue 1 https://doi.org/10.1002/anie.201507594	journal	December 2015
Experimental and Computational Studies of the Copper Borate Complexes [(NHC)Cu(HBEt ₃ )] and [(NHC)Cu(HB(C ₆ F ₅ ) ₃ )] Collins, Lee R.; Rajabi, Nasir A.; Macgregor, Stuart A. Angewandte Chemie International Edition, Vol. 55, Issue 50 https://doi.org/10.1002/anie.201608081	journal	November 2016
Spectroscopic Evidence for a Monomeric Copper(I) Hydride and Crystallographic Characterization of a Monomeric Silver(I) Hydride Romero, Erik A.; Olsen, Pauline M.; Jazzar, Rodolphe Angewandte Chemie International Edition, Vol. 56, Issue 14 https://doi.org/10.1002/anie.201700858	journal	March 2017
A Masked Cuprous Hydride as a Catalyst for Carbonyl Hydrosilylation in Aqueous Solutions Ritter, Florian; Mukherjee, Debabrata; Spaniol, Thomas P. Angewandte Chemie International Edition, Vol. 58, Issue 6 https://doi.org/10.1002/anie.201811890	journal	February 2019
Synthesis of a Room-Temperature-Stable Dimeric Copper(I) Hydride Frey, Guido D.; Donnadieu, Bruno; Soleilhavoup, Michele Chemistry - An Asian Journal, Vol. 6, Issue 2 https://doi.org/10.1002/asia.201000576	journal	October 2010
Bench-Stable Cobalt Pre-Catalysts for Mild Hydrosilative Reduction of Tertiary Amides to Amines and Beyond Nurseiit, Alibek; Janabel, Jaysan; Gudun, Kristina A. ChemCatChem, Vol. 11, Issue 2 https://doi.org/10.1002/cctc.201801605	journal	January 2019
Synthesis and Characterization of [Cu(NHC) 2 ]X Complexes: Catalytic and Mechanistic Studies of Hydrosilylation Reactions Díez-González, Silvia; Stevens, Edwin D.; Scott, Natalie M. Chemistry - A European Journal, Vol. 14, Issue 1 https://doi.org/10.1002/chem.200701013	journal	November 2007
Copper-Catalyzed Enantioselective Hydrogenation of Ketones Junge, Kathrin; Wendt, Bianca; Addis, Daniele Chemistry - A European Journal, Vol. 17, Issue 1 https://doi.org/10.1002/chem.201002311	journal	November 2010
Heterolysis of Dihydrogen by Silver Alkoxides and Fluorides Tate, Brandon K.; Nguyen, Jenna T.; Bacsa, John Chemistry - A European Journal, Vol. 21, Issue 28 https://doi.org/10.1002/chem.201500870	journal	June 2015
Mechanistic Studies on the Copper-Catalyzed Hydrosilylation of Ketones Issenhuth, Jean-Thomas; Notter, François-Paul; Dagorne, Samuel European Journal of Inorganic Chemistry, Vol. 2010, Issue 4 https://doi.org/10.1002/ejic.200900961	journal	February 2010
Fluoral hemiacetal, a new reagent for aromatic trifluoro alkylation Guy, A.; Lobgeois, A.; Lemaire, M. Journal of Fluorine Chemistry, Vol. 32, Issue 4 https://doi.org/10.1016/S0022-1139(00)81944-2	journal	September 1986
Simplified, “one-pot” procedure for the synthesis of [(Ph3P)CUH]6, a stable copper hydride for conjugate reductions Brestensky, Donna M.; Huseland, Dave E.; McGettigan, Colleen Tetrahedron Letters, Vol. 29, Issue 31 https://doi.org/10.1016/S0040-4039(00)82105-X	journal	January 1988
Hemiaminals of trifluoroacetaldehyde, as trifluoromethylating agents Mispelaere, Clotilde; Roques, Nicolas Tetrahedron Letters, Vol. 40, Issue 35 https://doi.org/10.1016/S0040-4039(99)01369-6	journal	August 1999
Coinage Metal Hydrides: Synthesis, Characterization, and Reactivity Jordan, Abraham J.; Lalic, Gojko; Sadighi, Joseph P. Chemical Reviews, Vol. 116, Issue 15 https://doi.org/10.1021/acs.chemrev.6b00366	journal	June 2016
Synthesis, Structural Characterization, and Gas-Phase Unimolecular Reactivity of Bis(diphenylphosphino)amino Copper Hydride Nanoclusters [Cu ₃ (X)(μ ₃ -H)((PPh ₂ ) ₂ NH) ₃ ](BF ₄ ), Where X = μ ₂ -Cl and μ ₃ -BH ₄ Li, Jiaye; White, Jonathan M.; Mulder, Roger J. Inorganic Chemistry, Vol. 55, Issue 19 https://doi.org/10.1021/acs.inorgchem.6b01696	journal	September 2016
Synthesis, Characterization, and Reactivity of the Group 11 Hydrido Clusters [Ag ₆ H ₄ (dppm) ₄ (OAc) ₂ ] and [Cu ₃ H(dppm) ₃ (OAc) ₂ ] Cook, Andrew W.; Nguyen, Thuy-Ai D.; Buratto, William R. Inorganic Chemistry, Vol. 55, Issue 23 https://doi.org/10.1021/acs.inorgchem.6b02385	journal	November 2016
Development of N-Heterocyclic Carbene–Copper Complexes for 1,3-Halogen Migration Schmid, Steven C.; Van Hoveln, Ryan; Rigoli, Jared W. Organometallics, Vol. 34, Issue 16 https://doi.org/10.1021/acs.organomet.5b00629	journal	August 2015
Synthesis and Reactivity of New Copper(I) Hydride Dimers Jordan, Abraham J.; Wyss, Chelsea M.; Bacsa, John Organometallics, Vol. 35, Issue 5 https://doi.org/10.1021/acs.organomet.6b00025	journal	February 2016
A Molecular Copper Catalyst for Hydrogenation of CO ₂ to Formate Zall, Christopher M.; Linehan, John C.; Appel, Aaron M. ACS Catalysis, Vol. 5, Issue 9 https://doi.org/10.1021/acscatal.5b01646	journal	August 2015
Alkene Hydrosilylation Using Tertiary Silanes with α-Diimine Nickel Catalysts. Redox-Active Ligands Promote a Distinct Mechanistic Pathway from Platinum Catalysts Pappas, Iraklis; Treacy, Sean; Chirik, Paul J. ACS Catalysis, Vol. 6, Issue 7 https://doi.org/10.1021/acscatal.6b01134	journal	May 2016
The Key Role of the Hemiaminal Intermediate in the Iron-Catalyzed Deaminative Hydrogenation of Amides Artús Suàrez, Lluís; Culakova, Zuzana; Balcells, David ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b02184	journal	August 2018
Highly Selective, Efficient Deoxygenative Hydrogenation of Amides Catalyzed by a Manganese Pincer Complex via Metal–Ligand Cooperation Zou, You-Quan; Chakraborty, Subrata; Nerush, Alexander ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b02902	journal	July 2018
Copper, Silver, and Gold Complexes in Hydrosilylation Reactions Díez-González, Silvia; Nolan, Steven P. Accounts of Chemical Research, Vol. 41, Issue 2 https://doi.org/10.1021/ar7001655	journal	February 2008
A survey of Hammett substituent constants and resonance and field parameters Hansch, Corwin.; Leo, A.; Taft, R. W. Chemical Reviews, Vol. 91, Issue 2 https://doi.org/10.1021/cr00002a004	journal	March 1991
CuH-Catalyzed Reactions Deutsch, Carl; Krause, Norbert; Lipshutz, Bruce H. Chemical Reviews, Vol. 108, Issue 8 https://doi.org/10.1021/cr0684321	journal	August 2008
Kinetic Isotope Effects in the Study of Organometallic Reaction Mechanisms Gómez-Gallego, Mar; Sierra, Miguel A. Chemical Reviews, Vol. 111, Issue 8 https://doi.org/10.1021/cr100436k	journal	August 2011
N-Heterocyclic Carbenes in Late Transition Metal Catalysis Díez-González, Silvia; Marion, Nicolas; Nolan, Steven P. Chemical Reviews, Vol. 109, Issue 8 https://doi.org/10.1021/cr900074m	journal	August 2009
A copper-(.mu.2-hydrogen) bond can be stronger than an intramolecular phosphorus .fwdarw. copper bond. Synthesis and structure of di-.mu.-hydridobis[.eta.2-1,1,1-tris(diphenylphosphinomethyl)ethane]dicopper Goeden, Gary V.; Huffman, John C.; Caulton, Kenneth G. Inorganic Chemistry, Vol. 25, Issue 15 https://doi.org/10.1021/ic00235a002	journal	July 1986
Synthesis and molecular geometry of hexameric triphenylphosphinocopper(I) hydride and the crystal structure of H6Cu6(PPh3)6. HCONMe2 [hexameric triphenylphosphino copper(I) hydride dimethylformamide] Churchill, Melvyn Rowen.; Bezman, Susan A.; Osborn, John A. Inorganic Chemistry, Vol. 11, Issue 8 https://doi.org/10.1021/ic50114a015	journal	August 1972
Kinetics of chromium(III)-chromium(II) electron transfer and equilibriums in the chromium(II)-acetate system Cannon, Roderick D.; Stillman, Jennifer S. Inorganic Chemistry, Vol. 14, Issue 9 https://doi.org/10.1021/ic50151a035	journal	September 1975
Kinetics of dissociation of the chromium(II) acetate dimer Cannon, Roderick D.; Stillman, Jennifer S. Inorganic Chemistry, Vol. 14, Issue 9 https://doi.org/10.1021/ic50151a036	journal	September 1975
A catalytic method for the reduction of esters to alcohols Berk, Scott C.; Kreutzer, Kristina A.; Buchwald, Stephen L. Journal of the American Chemical Society, Vol. 113, Issue 13 https://doi.org/10.1021/ja00013a074	journal	June 1991
A kinetic, mechanistic, and molecular mechanics investigation of olefin insertion into organoactinide-hydride bonds. Metal, olefin, ancillary ligand, and diastereoselection effects Lin, Zerong; Marks, Tobin J. Journal of the American Chemical Society, Vol. 112, Issue 14 https://doi.org/10.1021/ja00170a015	journal	July 1990
Hydride-mediated homogeneous catalysis. Catalytic reduction of .alpha.,.beta.-unsaturated ketones using [(Ph3P)CuH]6 and H2 Mahoney, Wayne S.; Stryker, Jeffrey M. Journal of the American Chemical Society, Vol. 111, Issue 24 https://doi.org/10.1021/ja00206a008	journal	November 1989
Selective hydride-mediated conjugate reduction of .alpha.,.beta.-unsaturated carbonyl compounds using [(Ph3P)CuH]6 Mahoney, Wayne S.; Brestensky, Donna M.; Stryker, Jeffrey M. Journal of the American Chemical Society, Vol. 110, Issue 1 https://doi.org/10.1021/ja00209a048	journal	January 1988
Hydrogen Transfer to Carbonyls and Imines from a Hydroxycyclopentadienyl Ruthenium Hydride: Evidence for Concerted Hydride and Proton Transfer Casey, Charles P.; Singer, Steven W.; Powell, Douglas R. Journal of the American Chemical Society, Vol. 123, Issue 6 https://doi.org/10.1021/ja002177z	journal	February 2001
Soluble copper hydrides: solution behavior and reactions related to carbon monoxide hydrogenation Goeden, Gary V.; Caulton, Kenneth G. Journal of the American Chemical Society, Vol. 103, Issue 24 https://doi.org/10.1021/ja00414a062	journal	December 1981
Mechanism of thermal decomposition of n-butyl(tri-n-butylphosphine) copper(I) Whitesides, George M.; Stedronsky, Erwin R.; Casey, Charles P. Journal of the American Chemical Society, Vol. 92, Issue 5 https://doi.org/10.1021/ja00708a067	journal	March 1970
Preparation and crystallographic characterization of a hexameric triphenylphosphinecopper hydride cluster Bezman, Susan A.; Churchill, Melvyn R.; Osborn, John A. Journal of the American Chemical Society, Vol. 93, Issue 8 https://doi.org/10.1021/ja00737a045	journal	April 1971
Nature of soluble copper(I) hydride Dilts, J. A.; Shriver, D. F. Journal of the American Chemical Society, Vol. 90, Issue 21 https://doi.org/10.1021/ja01023a020	journal	October 1968
Cryoscopic study of copper(I) hydride-phosphine complexes Dilts, J. A.; Shriver, Duward F. Journal of the American Chemical Society, Vol. 91, Issue 15 https://doi.org/10.1021/ja01043a013	journal	July 1969
Reaction of copper(I) hydride with organocopper(I) compounds Whitesides, George M.; San Filippo, Joseph; Stredronsky, Erwin R. Journal of the American Chemical Society, Vol. 91, Issue 23 https://doi.org/10.1021/ja01051a093	journal	November 1969
Basicity of Nucleophilic Carbenes in Aqueous and Nonaqueous SolventsTheoretical Predictions Magill, Alison M.; Cavell, Kingsley J.; Yates, Brian F. Journal of the American Chemical Society, Vol. 126, Issue 28 https://doi.org/10.1021/ja038973x	journal	July 2004
Copper-Catalyzed Recycling of Halogen Activating Groups via 1,3-Halogen Migration Grigg, R. David; Van Hoveln, Ryan; Schomaker, Jennifer M. Journal of the American Chemical Society, Vol. 134, Issue 39 https://doi.org/10.1021/ja306446m	journal	September 2012
A Nanospheric Polyhydrido Copper Cluster of Elongated Triangular Orthobicupola Array: Liberation of H ₂ from Solar Energy Dhayal, Rajendra S.; Liao, Jian-Hong; Lin, Yan-Ru Journal of the American Chemical Society, Vol. 135, Issue 12 https://doi.org/10.1021/ja401576s	journal	March 2013
Electron Transfer from Hexameric Copper Hydrides Eberhart, Michael S.; Norton, Jack R.; Zuzek, Ashley Journal of the American Chemical Society, Vol. 135, Issue 46 https://doi.org/10.1021/ja408925m	journal	November 2013
Catalytic Anti-Markovnikov Hydrobromination of Alkynes Uehling, Mycah R.; Rucker, Richard P.; Lalic, Gojko Journal of the American Chemical Society, Vol. 136, Issue 24 https://doi.org/10.1021/ja503944n	journal	June 2014
Mechanistic Studies of Copper(I)-Catalyzed 1,3-Halogen Migration Van Hoveln, Ryan; Hudson, Brandi M.; Wedler, Henry B. Journal of the American Chemical Society, Vol. 137, Issue 16 https://doi.org/10.1021/ja511236d	journal	April 2015
Copper-Catalyzed Hydroalkylation of Terminal Alkynes Uehling, Mycah R.; Suess, Alison M.; Lalic, Gojko Journal of the American Chemical Society, Vol. 137, Issue 4 https://doi.org/10.1021/ja5124368	journal	January 2015
Isotope Effects on Hydride Transfer Reactions from Transition Metal Hydrides to Trityl Cation. An Inverse Isotope Effect for a Hydride Transfer Cheng, Tan-Yun; Bullock, R. Morris Journal of the American Chemical Society, Vol. 121, Issue 13 https://doi.org/10.1021/ja983448x	journal	April 1999
Mechanism of Copper-Catalyzed Hydroalkylation of Alkynes: An Unexpected Role of Dinuclear Copper Complexes Suess, Alison M.; Uehling, Mycah R.; Kaminsky, Werner Journal of the American Chemical Society, Vol. 137, Issue 24 https://doi.org/10.1021/jacs.5b03086	journal	June 2015
Design of Modified Amine Transfer Reagents Allows the Synthesis of α-Chiral Secondary Amines via CuH-Catalyzed Hydroamination Niu, Dawen; Buchwald, Stephen L. Journal of the American Chemical Society, Vol. 137, Issue 30 https://doi.org/10.1021/jacs.5b05446	journal	July 2015
A Cu ₂₅ Nanocluster with Partial Cu(0) Character Nguyen, Thuy-Ai D.; Jones, Zachary R.; Goldsmith, Bryan R. Journal of the American Chemical Society, Vol. 137, Issue 41 https://doi.org/10.1021/jacs.5b07574	journal	October 2015
Mechanistic Studies Lead to Dramatically Improved Reaction Conditions for the Cu-Catalyzed Asymmetric Hydroamination of Olefins Bandar, Jeffrey S.; Pirnot, Michael T.; Buchwald, Stephen L. Journal of the American Chemical Society, Vol. 137, Issue 46 https://doi.org/10.1021/jacs.5b10219	journal	November 2015
Triphosphine-Ligated Copper Hydrides for CO ₂ Hydrogenation: Structure, Reactivity, and Thermodynamic Studies Zall, Christopher M.; Linehan, John C.; Appel, Aaron M. Journal of the American Chemical Society, Vol. 138, Issue 31 https://doi.org/10.1021/jacs.6b05349	journal	August 2016
Catalytic Anti-Markovnikov Hydroallylation of Terminal and Functionalized Internal Alkynes: Synthesis of Skipped Dienes and Trisubstituted Alkenes Mailig, Melrose; Hazra, Avijit; Armstrong, Megan K. Journal of the American Chemical Society, Vol. 139, Issue 20 https://doi.org/10.1021/jacs.7b02104	journal	May 2017
A Thorium Chalcogenolate Series Generated by Atom Insertion into Thorium–Carbon Bonds Settineri, Nicholas S.; Garner, Mary E.; Arnold, John Journal of the American Chemical Society, Vol. 139, Issue 17 https://doi.org/10.1021/jacs.7b02356	journal	April 2017
Mechanistic Studies of Copper-Catalyzed Asymmetric Hydroboration of Alkenes Xi, Yumeng; Hartwig, John F. Journal of the American Chemical Society, Vol. 139, Issue 36 https://doi.org/10.1021/jacs.7b07124	journal	September 2017
Diastereodivergent Reductive Cross Coupling of Alkynes through Tandem Catalysis: Z - and E -Selective Hydroarylation of Terminal Alkynes Armstrong, Megan K.; Goodstein, Madison B.; Lalic, Gojko Journal of the American Chemical Society, Vol. 140, Issue 32 https://doi.org/10.1021/jacs.8b05113	journal	July 2018
CuH-Catalyzed Enantioselective Ketone Allylation with 1,3-Dienes: Scope, Mechanism, and Applications Li, Chengxi; Liu, Richard Y.; Jesikiewicz, Luke T. Journal of the American Chemical Society, Vol. 141, Issue 12 https://doi.org/10.1021/jacs.9b01784	journal	February 2019
Reduction of benzophenone with metal hydrides. A kinetic isotope effect and substituent effect study Yamataka, Hiroshi; Hanafusa, Terukiyo The Journal of Organic Chemistry, Vol. 53, Issue 4 https://doi.org/10.1021/jo00239a014	journal	February 1988
Unusual kinetics for the hydroboration of alkenes with 9-borabicyclo[3.3.1]nonane Brown, Herbert C.; Scouten, Charles G.; Wang, Kung K. The Journal of Organic Chemistry, Vol. 44, Issue 14 https://doi.org/10.1021/jo01328a061	journal	July 1979
A Simple and Efficient Copper-Catalyzed Procedure for the Hydrosilylation of Hindered and Functionalized Ketones Díez-González, Silvia; Kaur, Harneet; Zinn, Fabiano Kauer The Journal of Organic Chemistry, Vol. 70, Issue 12 https://doi.org/10.1021/jo050397v	journal	June 2005
New Stable Reagents for the Nucleophilic Trifluoromethylation. 1. Trifluoromethylation of Carbonyl Compounds with N -Formylmorpholine Derivatives Billard, T.; Bruns, S.; Langlois, B. R. Organic Letters, Vol. 2, Issue 14 https://doi.org/10.1021/ol005987o	journal	July 2000
Asymmetric Hydrogenation of Aryl Ketones Mediated by a Copper Catalyst Shimizu, Hideo; Igarashi, Daisuke; Kuriyama, Wataru Organic Letters, Vol. 9, Issue 9 https://doi.org/10.1021/ol070289q	journal	April 2007
Copper-Catalyzed Asymmetric Hydrogenation of Aryl and Heteroaryl Ketones Krabbe, Scott W.; Hatcher, Mark A.; Bowman, Roy K. Organic Letters, Vol. 15, Issue 17 https://doi.org/10.1021/ol4021223	journal	August 2013
(NHC)Cu ^I (NHC = N-Heterocyclic Carbene) Complexes as Efficient Catalysts for the Reduction of Carbonyl Compounds Kaur, Harneet; Zinn, Fabiano Kauer; Stevens, Edwin D. Organometallics, Vol. 23, Issue 5 https://doi.org/10.1021/om034285a	journal	March 2004
Synthesis, Structure, and Alkyne Reactivity of a Dimeric (Carbene)copper(I) Hydride Mankad, Neal P.; Laitar, David S.; Sadighi, Joseph P. Organometallics, Vol. 23, Issue 14, p. 3369-3371 https://doi.org/10.1021/om0496380	journal	July 2004
Cyclopentadienyl and Olefin Substituent Effects on Insertion and β-Hydrogen Elimination with Group 4 Metallocenes. Kinetics, Mechanism, and Thermodynamics for Zirconocene and Hafnocene Alkyl Hydride Derivatives Chirik, Paul J.; Bercaw, John E. Organometallics, Vol. 24, Issue 22 https://doi.org/10.1021/om0580351	journal	October 2005
Cationic Copper(I) Complexes as Efficient Precatalysts for the Hydrosilylation of Carbonyl Compounds Díez-González, Silvia; Scott, Natalie M.; Nolan, Steven P. Organometallics, Vol. 25, Issue 9 https://doi.org/10.1021/om0600487	journal	April 2006
Hydrosilylation of Carbonyl-Containing Substrates Catalyzed by an Electrophilic η ¹ -Silane Iridium(III) Complex Park, Sehoon; Brookhart, Maurice Organometallics, Vol. 29, Issue 22 https://doi.org/10.1021/om100818y	journal	November 2010
Bulky N -Heterocyclic Carbene IPr* in Selected Organo- and Transition Metal-Mediated Catalytic Applications Balogh, János; Slawin, Alexandra M. Z.; Nolan, Steven P. Organometallics, Vol. 31, Issue 8 https://doi.org/10.1021/om300104j	journal	March 2012
Mechanistic Insight into the (NHC)copper(I)-Catalyzed Hydrosilylation of Ketones Vergote, Thomas; Nahra, Fady; Merschaert, Alain Organometallics, Vol. 33, Issue 8 https://doi.org/10.1021/om401097q	journal	April 2014
Towards the online computer-aided design of catalytic pockets Falivene, Laura; Cao, Zhen; Petta, Andrea Nature Chemistry, Vol. 11, Issue 10 https://doi.org/10.1038/s41557-019-0319-5	journal	September 2019
Tandem copper hydride–Lewis pair catalysed reduction of carbon dioxide into formate with dihydrogen Romero, Erik A.; Zhao, Tianxiang; Nakano, Ryo Nature Catalysis, Vol. 1, Issue 10 https://doi.org/10.1038/s41929-018-0140-3	journal	October 2018
Copper-catalyzed asymmetric hydrogenation of 2-substituted ketones via dynamic kinetic resolution Zatolochnaya, Olga V.; Rodríguez, Sonia; Zhang, Yongda Chemical Science, Vol. 9, Issue 19 https://doi.org/10.1039/C8SC00434J	journal	January 2018
A new alternative to Stryker's reagent in hydrosilylation: synthesis, structure, and reactivity of a well-defined carbene–copper(ii) acetate complex Yun, Jaesook; Kim, Daesung; Yun, Hoseop Chemical Communications, Issue 41 https://doi.org/10.1039/b509964a	journal	January 2005
New catalyst systems for iron-catalyzed hydrosilane reduction of carboxamides Tsutsumi, Hironori; Sunada, Yusuke; Nagashima, Hideo Chemical Communications, Vol. 47, Issue 23 https://doi.org/10.1039/c1cc10636h	journal	January 2011
A general and selective copper-catalyzed reduction of secondary amides Das, Shoubhik; Join, Benoît; Junge, Kathrin Chemical Communications, Vol. 48, Issue 21 https://doi.org/10.1039/c2cc17209g	journal	January 2012
Regioselective transformation of alkynes catalyzed by a copper hydride or boryl copper species Fujihara, Tetsuaki; Semba, Kazuhiko; Terao, Jun Catalysis Science & Technology, Vol. 4, Issue 6 https://doi.org/10.1039/c4cy00070f	journal	January 2014
Stabilization of Labile Carbonyl Addition Intermediates by a Synthetic Receptor Iwasawa, T.; Hooley, R. J.; Rebek, J. Science, Vol. 317, Issue 5837 https://doi.org/10.1126/science.1143272	journal	July 2007
Catalytic asymmetric hydroamination of unactivated internal olefins to aliphatic amines Yang, Yang; Shi, Shi-Liang; Niu, Dawen Science, Vol. 349, Issue 6243 https://doi.org/10.1126/science.aab3753	journal	July 2015
Copper-catalyzed asymmetric addition of olefin-derived nucleophiles to ketones Yang, Y.; Perry, I. B.; Lu, G. Science, Vol. 353, Issue 6295 https://doi.org/10.1126/science.aaf7720	journal	June 2016
Carbonyl Addition Reactions: Factors Affecting the Hydrate–Hemiacetal and Hemiacetal–Acetal Equilibrium Constants Guthrie, J. Peter Canadian Journal of Chemistry, Vol. 53, Issue 6 https://doi.org/10.1139/v75-125	journal	March 1975

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