Copper-catalyzed dehydrogenative borylation of terminal alkynes with pinacolborane

Romero, Erik A.; Jazzar, Rodolphe; Bertrand, Guy

doi:10.1039/c6sc02668k

Title: Copper-catalyzed dehydrogenative borylation of terminal alkynes with pinacolborane

Journal Article · Tue Aug 09 00:00:00 EDT 2016 · Chemical Science

DOI:https://doi.org/10.1039/c6sc02668k· OSTI ID:1465712

Romero, Erik A. ^[1]; Jazzar, Rodolphe ^[1]; Bertrand, Guy ^[1]

University of California San Diego, La Jolla, CA (United States). UCSD-CNRS Joint Research Chemistry Laboratory (UMI 3555), Department of Chemistry and Biochemistry

LCuOTf complexes [L = cyclic (alkyl)(amino)carbenes (CAACs) or N-heterocyclic carbenes (NHCs)] selectively promote the dehydrogenative borylation of C(sp)–H bonds at room temperature. It is shown that σ,π-bis(copper) acetylide and copper hydride complexes are the key catalytic species.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Univ. of California, San Diego, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-13ER16370; SC0009376

OSTI ID:: 1465712

Journal Information:: Chemical Science, Vol. 8, Issue 1; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 55 works

Citation information provided by
Web of Science

References (43)

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
Adaptability of the SiNN Pincer Ligand in Iridium and Rhodium Complexes Relevant to Borylation Catalysis Lee, Chun-I; Hirscher, Nathanael A.; Zhou, Jia Organometallics, Vol. 34, Issue 13 https://doi.org/10.1021/acs.organomet.5b00125	journal	March 2015
Selection of boron reagents for Suzuki–Miyaura coupling Lennox, Alastair J. J.; Lloyd-Jones, Guy C. Chem. Soc. Rev., Vol. 43, Issue 1 https://doi.org/10.1039/C3CS60197H	journal	January 2014
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
Imidazolylidenes, imidazolinylidenes and imidazolidines Arduengo, Anthony J.; Krafczyk, Roland; Schmutzler, Reinhard Tetrahedron, Vol. 55, Issue 51 https://doi.org/10.1016/S0040-4020(99)00927-8	journal	December 1999
Direct Evidence of a Dinuclear Copper Intermediate in Cu(I)-Catalyzed Azide-Alkyne Cycloadditions Worrell, B. T.; Malik, J. A.; Fokin, V. V. Science, Vol. 340, Issue 6131 https://doi.org/10.1126/science.1229506	journal	April 2013
Copper-Catalyzed Highly Selective Semihydrogenation of Non-Polar Carbon-Carbon Multiple Bonds using a Silane and an Alcohol Semba, Kazuhiko; Fujihara, Tetsuaki; Xu, Tinghua Advanced Synthesis & Catalysis, Vol. 354, Issue 8 https://doi.org/10.1002/adsc.201200200	journal	May 2012
Recent developments in alkyne borylations Barbeyron, Renaud; Benedetti, Erica; Cossy, Janine Tetrahedron, Vol. 70, Issue 45 https://doi.org/10.1016/j.tet.2014.06.026	journal	November 2014
A Comparison of the Stability and Reactivity of Diamido‐ and Diaminocarbene Copper Alkoxide and Hydride Complexes Collins, Lee R.; Riddlestone, Ian M.; Mahon, Mary F. Chemistry – A European Journal, Vol. 21, Issue 40 https://doi.org/10.1002/chem.201502476	journal	August 2015
Catalytic dehydrogenative borylation of terminal alkynes by POCOP-supported palladium complexes Pell, Christopher J.; Ozerov, Oleg V. Inorganic Chemistry Frontiers, Vol. 2, Issue 8 https://doi.org/10.1039/C5QI00074B	journal	January 2015
Enhanced Reactivity of Dinuclear Copper(I) Acetylides in Dipolar Cycloadditions Ahlquist, Mårten; Fokin, Valery V. Organometallics, Vol. 26, Issue 18 https://doi.org/10.1021/om700669v	journal	August 2007
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
Remarkably Selective Iridium Catalysts for the Elaboration of Aromatic C-H Bonds Cho, J. -Y. Science, Vol. 295, Issue 5553 https://doi.org/10.1126/science.1067074	journal	November 2001
The Janus Face of the X Ligand in the Copper-Catalyzed Azide–Alkyne Cycloaddition Jin, Liqun; Romero, Erik A.; Melaimi, Mohand Journal of the American Chemical Society, Vol. 137, Issue 50 https://doi.org/10.1021/jacs.5b11028	journal	December 2015
Regioselectivity of the borylation of alkanes and arenes Hartwig, John F. Chemical Society Reviews, Vol. 40, Issue 4 https://doi.org/10.1039/c0cs00156b	journal	January 2011
Catalytic Dehydrogenative Borylation of Terminal Alkynes by a SiNN Pincer Complex of Iridium Lee, Chun-I; Zhou, Jia; Ozerov, Oleg V. Journal of the American Chemical Society, Vol. 135, Issue 9 https://doi.org/10.1021/ja311682c	journal	February 2013
Isolation of bis(copper) key intermediates in Cu-catalyzed azide-alkyne “click reaction” Jin, Liqun; Tolentino, Daniel R.; Melaimi, Mohand Science Advances, Vol. 1, Issue 5 https://doi.org/10.1126/sciadv.1500304	journal	June 2015
NHC–copper hydrides as chemoselective reducing agents: catalytic reduction of alkynes, alkyl triflates, and alkyl halides Cox, Nick; Dang, Hester; Whittaker, Aaron M. Tetrahedron, Vol. 70, Issue 27-28 https://doi.org/10.1016/j.tet.2014.04.004	journal	July 2014
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
Cyclic (Alkyl)(Amino)Carbenes (CAACs): Stable Carbenes on the Rise Soleilhavoup, Michèle; Bertrand, Guy Accounts of Chemical Research, Vol. 48, Issue 2 https://doi.org/10.1021/ar5003494	journal	December 2014
Synthesis of Triborylalkenes from Terminal Alkynes by Iridium-Catalyzed Tandem CH Borylation and Diboration Lee, Chun-I; Shih, Wei-Chun; Zhou, Jia Angewandte Chemie International Edition, Vol. 54, Issue 47 https://doi.org/10.1002/anie.201507372	journal	October 2015
Copper N-heterocyclic carbene complexes in catalysis Egbert, Jonathan D.; Cazin, Catherine S. J.; Nolan, Steven P. Catalysis Science & Technology, Vol. 3, Issue 4 https://doi.org/10.1039/c2cy20816d	journal	January 2013
Copper(I)-Catalyzed Synthesis of Azoles. DFT Study Predicts Unprecedented Reactivity and Intermediates Himo, Fahmi; Lovell, Timothy; Hilgraf, Robert Journal of the American Chemical Society, Vol. 127, Issue 1 https://doi.org/10.1021/ja0471525	journal	January 2005
Bonding and Reactivity of a μ-Hydrido Dicopper Cation Wyss, Chelsea M.; Tate, Brandon K.; Bacsa, John Angewandte Chemie International Edition, Vol. 52, Issue 49 https://doi.org/10.1002/anie.201306736	journal	October 2013
Intramolecular “Hydroiminiumation” of Alkenes: Application to the Synthesis of Conjugate Acids of Cyclic Alkyl Amino Carbenes (CAACs) Jazzar, Rodolphe; Dewhurst, Rian D.; Bourg, Jean-Baptiste Angewandte Chemie International Edition, Vol. 46, Issue 16 https://doi.org/10.1002/anie.200605083	journal	April 2007
A Fluxional Copper Acetylide Cluster in CuAAC Catalysis Makarem, Ata; Berg, Regina; Rominger, Frank Angewandte Chemie International Edition, Vol. 54, Issue 25 https://doi.org/10.1002/anie.201502368	journal	April 2015
Stable Cyclic (Alkyl)(Amino)Carbenes as Rigid or Flexible, Bulky, Electron-Rich Ligands for Transition-Metal Catalysts: A Quaternary Carbon Atom Makes the Difference Lavallo, Vincent; Canac, Yves; Präsang, Carsten Angewandte Chemie International Edition, Vol. 44, Issue 35, p. 5705-5709 https://doi.org/10.1002/anie.200501841	journal	September 2005
Thermal, Catalytic, Regiospecific Functionalization of Alkanes Chen, H. Science, Vol. 287, Issue 5460 https://doi.org/10.1126/science.287.5460.1995	journal	March 2000
A Brief Survey of Our Contribution to Stable Carbene Chemistry Martin, David; Melaimi, Mohand; Soleilhavoup, Michele Organometallics, Vol. 30, Issue 20 https://doi.org/10.1021/om200650x	journal	October 2011
Borylation and Silylation of C–H Bonds: A Platform for Diverse C–H Bond Functionalizations Hartwig, John F. Accounts of Chemical Research, Vol. 45, Issue 6 https://doi.org/10.1021/ar200206a	journal	November 2011
Isolation of a Copper(I) Triazolide: A “Click” Intermediate Nolte, Christoph; Mayer, Peter; Straub, Bernd F. Angewandte Chemie International Edition, Vol. 46, Issue 12 https://doi.org/10.1002/anie.200604444	journal	March 2007
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
Ligand survey results in identification of PNP pincer complexes of iridium as long-lived and chemoselective catalysts for dehydrogenative borylation of terminal alkynes Lee, Chun-I; DeMott, Jessica C.; Pell, Christopher J. Chemical Science, Vol. 6, Issue 11 https://doi.org/10.1039/C5SC02161H	journal	January 2015
C−H Activation for the Construction of C−B Bonds Mkhalid, Ibraheem A. I.; Barnard, Jonathan H.; Marder, Todd B. Chemical Reviews, Vol. 110, Issue 2 https://doi.org/10.1021/cr900206p	journal	February 2010
Alkynylboranes: A Practical Approach by Zinc-Catalyzed Dehydrogenative Coupling of Terminal Alkynes with 1,8-Naphthalenediaminatoborane Tsuchimoto, Teruhisa; Utsugi, Hirokazu; Sugiura, Tetsuya Advanced Synthesis & Catalysis, Vol. 357, Issue 1 https://doi.org/10.1002/adsc.201400767	journal	November 2014
Stable Cyclic Carbenes and Related Species beyond Diaminocarbenes Melaimi, Mohand; Soleilhavoup, Michèle; Bertrand, Guy Angewandte Chemie International Edition, Vol. 49, Issue 47 https://doi.org/10.1002/anie.201000165	journal	September 2010
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
µ-Acetylide and µ-alkenylidene ligands in “click” triazole syntheses Straub, Bernd F. Chemical Communications, Issue 37 https://doi.org/10.1039/b706926j	journal	January 2007
Mechanism of the Ligand-Free CuI-Catalyzed Azide-Alkyne Cycloaddition Reaction Rodionov, Valentin O.; Fokin, Valery V.; Finn, M. G. Angewandte Chemie International Edition, Vol. 44, Issue 15 https://doi.org/10.1002/anie.200461496	journal	April 2005
Rediscovering Organocopper Chemistry Through Copper Hydride. It’s All About the Ligand Lipshutz, Bruce Synlett, Vol. 2009, Issue 04 https://doi.org/10.1055/s-0028-1087923	journal	February 2009
Copper-Catalyzed Hydrofunctionalization of Alkynes Suess, Alison; Lalic, Gojko Synlett, Vol. 27, Issue 08 https://doi.org/10.1055/s-0035-1561357	journal	March 2016
CuH in a Bottle: A Convenient Reagent for Asymmetric Hydrosilylations Lipshutz, Bruce H.; Frieman, Bryan A. Angewandte Chemie International Edition, Vol. 44, Issue 39 https://doi.org/10.1002/anie.200500800	journal	October 2005
Intramolecular “Hydroiminiumation and -amidiniumation” of Alkenes: A Convenient, Flexible, and Scalable Route to Cyclic Iminium and Imidazolinium Salts Jazzar, Rodolphe; Bourg, Jean-Baptiste; Dewhurst, Rian D. The Journal of Organic Chemistry, Vol. 72, Issue 9 https://doi.org/10.1021/jo0703909	journal	April 2007

Cited By (12)

Cyclische Alkylaminocarbene (CAACs): Neues von guten Bekannten Melaimi, Mohand; Jazzar, Rodolphe; Soleilhavoup, Michèle Angewandte Chemie, Vol. 129, Issue 34 https://doi.org/10.1002/ange.201702148	journal	June 2017
Kupfer‐katalysierte Triborierung terminaler Alkine mit B ₂ pin ₂ : Effiziente Synthese von 1,1,2‐Triborylalkenen Liu, Xiaocui; Ming, Wenbo; Friedrich, Alexandra Angewandte Chemie, Vol. 132, Issue 1 https://doi.org/10.1002/ange.201908466	journal	November 2019
Kupferkatalysierte Triborierung: Einfache, atomökonomische Synthese von 1,1,1‐Triborylalkanen aus terminalen Alkinen und HBpin Liu, Xiaocui; Ming, Wenbo; Zhang, Yixiao Angewandte Chemie, Vol. 131, Issue 52 https://doi.org/10.1002/ange.201909376	journal	November 2019
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
Cyclic (Alkyl)(amino)carbenes (CAACs): Recent Developments Melaimi, Mohand; Jazzar, Rodolphe; Soleilhavoup, Michèle Angewandte Chemie International Edition, Vol. 56, Issue 34 https://doi.org/10.1002/anie.201702148	journal	June 2017
Copper‐Catalyzed Triboration of Terminal Alkynes Using B ₂ pin ₂ : Efficient Synthesis of 1,1,2‐Triborylalkenes Liu, Xiaocui; Ming, Wenbo; Friedrich, Alexandra Angewandte Chemie International Edition, Vol. 59, Issue 1 https://doi.org/10.1002/anie.201908466	journal	November 2019
Copper‐Catalyzed Triboration: Straightforward, Atom‐Economical Synthesis of 1,1,1‐Triborylalkanes from Terminal Alkynes and HBpin Liu, Xiaocui; Ming, Wenbo; Zhang, Yixiao Angewandte Chemie International Edition, Vol. 58, Issue 52 https://doi.org/10.1002/anie.201909376	journal	December 2019
Large CuI8 chalcogenone cubic cages with non-interacting counter ions Katam, Srinivas; Ganesan, Prabusankar Dalton Transactions, Vol. 46, Issue 47 https://doi.org/10.1039/c7dt03796a	journal	January 2017
The debut of chiral cyclic (alkyl)(amino)carbenes (CAACs) in enantioselective catalysis Pichon, Delphine; Soleilhavoup, Michele; Morvan, Jennifer Chemical Science, Vol. 10, Issue 33 https://doi.org/10.1039/c9sc02810b	journal	January 2019
N-Heterocyclic Carbene Adducts of Alkynyl Functionalized 1,3,2-Dithioborolanes Böser, Richard; Denker, Lars; Frank, René Molecules, Vol. 24, Issue 9 https://doi.org/10.3390/molecules24091690	journal	April 2019
Kupferkatalysierte Triborierung: Einfache, atomökonomische Synthese von 1,1,1-Triborylalkanen aus terminalen Alkinen und HBpin Liu, Xiaocui; Ming, Wenbo; Zhang, Yixiao FID GEO https://doi.org/10.23689/fidgeo-4817	text	January 2019
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

Similar Records

(CAAC)CuX-catalyzed hydroboration of terminal alkynes with pinacolborane directed by the X-ligand

Journal Article · Wed Sep 28 00:00:00 EDT 2016 · Journal of Organometallic Chemistry · OSTI ID:1465712

Romero, Erik A.; Jazzar, Rodolphe; Bertrand, Guy

Cyclic (Alkyl)- and (Aryl)-(amino)carbene Coinage Metal Complexes and Their Applications

Journal Article · Thu Apr 02 00:00:00 EDT 2020 · Chemical Reviews · OSTI ID:1465712

Jazzar, Rodolphe; Soleilhavoup, Michele; Bertrand, Guy

Cyclic (Alkyl)(amino)carbene Ligands Enable Cu‐Catalyzed Markovnikov Protoboration and Protosilylation of Terminal Alkynes: A Versatile Portal to Functionalized Alkenes**

Journal Article · Thu Jul 29 00:00:00 EDT 2021 · Angewandte Chemie · OSTI ID:1465712

Gao, Yang; Yazdani, Sima; Kendrick, IV, Aaron; +6 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Copper-catalyzed dehydrogenative borylation of terminal alkynes with pinacolborane

Citation Formats

References (43)

Cited By (12)

Similar Records

Related Subjects