Gao, Yang; Yazdani, Sima; Kendrick, Aaron, IV; Junor, Glen P.; Kang, Taeho; Grotjahn, Douglas B.; Bertrand, Guy; Jazzar, Rodolphe; Engle, Keary M. (2021). Data from: Cyclic(Alkyl)(Amino)Carbene Ligands Enable Cu-Catalyzed Markovnikov Protoboration and Protosilylation of Terminal Alkynes: A Versatile Portal to Functionalized Alkenes. UC San Diego Library Digital Collections. https://doi.org/10.6075/J00P0XK4

Abstract: Regioselective hydrofunctionalization of alkynes represents a straightforward route to access alkenyl boronate and silane building blocks. In previously reported catalytic systems, high selectivity is achieved with a limited scope of substrates and/or reagents, with general solutions lacking. Herein, we describe a selective copper-catalyzed Markovnikov hydrofunctionalization of terminal alkynes that is facilitated by strongly donating cyclic(alkyl)(amino)carbene (CAAC) ligands. Using this method, both alkyl and aryl-substituted alkynes are coupled with a variety of boryl and silyl reagents with high α-selectivity. The reaction is scalable, and the products are versatile intermediates that can participate in various downstream transformations. Preliminary mechanistic experiments shed light on the role of CAAC ligands in this process.

• 2020 to 2021

• 2021

• Gao, Yang
• Grotjahn, Douglas B.
• Junor, Glen P.
• Kang, Taeho
• Kendrick, Aaron, IV
• Yazdani, Sima

• Engle, Keary M.

• Bertrand, Guy
• Jazzar, Rodolphe

This work was financially supported by the National Institute of Health (5R35GM125052-04 and diversity supplement, 5R35GM125052-04S1) and an ACS PRF Doctoral New Investigator Grant (K.M.E.). We gratefully acknowledge the Kwanjeong Educational Foundation (Graduate Fellowship to T.K.). This work was also supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Catalysis Science Program, under Award No. DE-SC0009376 (G.B.), National Science Foundation Award No. CHE-1800598 (D.B.G.) and the Agence Nationale de la Recherche Award No. ANR-19-276 CE07-0017 (R.J). Thanks are due to San Diego State University for initial support of this work by a SDSU University Graduate Fellowship (S.Y.) and the Alfred P. Sloan Foundations University Centre for Exemplary Mentoring (G.P.J.). This material is based upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE- 1650112 (G.P.J.). We also acknowledge the Keck Foundation for provided computational resources.

• Alkyne functionalization
• Copper catalysis
• Cyclic (alkyl)(amino)carbenes (CAAC)
• Markovnikov selectivity
• Protoboration
• Protosilylation

• data

• No linguistic content; Not applicable

Identifier: Douglas B. Grotjahn: https://orcid.org/0000-0002-2481-7889

Identifier: Glen P. Junor: https://orcid.org/0000-0002-6733-3577

Identifier: Guy Bertrand: https://orcid.org/0000-0003-2623-2363

Identifier: Keary M. Engle: https://orcid.org/0000-0003-2767-6556

Identifier: Rodolphe Jazzar: https://orcid.org/0000-0002-4156-7826

Identifier: Sima Yazdani: https://orcid.org/0000-0003-0261-7146

Identifier: Taeho Kang: https://orcid.org/0000-0003-4549-262X

Identifier: Yang Gao: https://orcid.org/0000-0001-9270-6251

Primary associated publication

• Gao, Yang; Yazdani, Sima; Kendrick, Aaron; Junor, Glen; Grotjahn, Douglas; Bertrand, Guy; Jazzar, Rodolphe, Engle, Keary. (2021): Cyclic(Alkyl)(Amino)Carbene Ligands Enable Cu-Catalyzed Markovnikov Protoboration and Protosilylation of Terminal Alkynes: A Versatile Portal to Functionalized Alkenes. ChemRxiv. Preprint. https://doi.org/10.26434/chemrxiv.14368607.v1
• Y. Gao, S. Yazdani, A. Kendrick, G. P. Junor, T. Kang, D. B. Grotjahn, G. Bertrand, R. Jazzar, K. M. Engle. Cyclic (Alkyl)(amino)carbene Ligands Enable Cu-Catalyzed Markovnikov Protoboration and Protosilylation of Terminal Alkynes: A Versatile Portal to Functionalized Alkenes. Angew. Chem. Int. Ed. 2021, 60, 19871. https://doi.org/10.1002/anie.202106107

Software

• Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2013.
• Gaussian 16, Revision C.01, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A. V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa,J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian, Inc., Wallingford CT, 2016.

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2023-06-30