Data from: Cyclic(Alkyl)(Amino)Carbene Ligands Enable Cu-Catalyzed Markovnikov Protoboration and Protosilylation of Terminal Alkynes: A Versatile Portal to Functionalized Alkenes
AdCAAC5
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Description | All DFT calculations pertaining to CAAC5 with nitrogen bearing a diisopropylphenyl substituent and an adamantyl group containing the quaternary carbon alpha to carbene center. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory with ultrafine integration grids. The .chk, .fchk, and .log files are included for all calculations. |
Technical Details | Calculations were performed in Gaussian09 |
SAdNHC5
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Description | All DFT calculations pertaining to saturated NHC bearing an adamantyl group on each nitrogen. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory with ultrafine integration grids. The .chk, .fchk, and .log files are included for all calculations. |
Technical Details | Calculations were performed in Gaussian16 |
iPrBiCAAC
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Description | All DFT calculations pertaining to BiCAAC with nitrogen bearing a diisopropylphenyl substituent and an isopropyl group on the quaternary carbon alpha to carbene center. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory with ultrafine integration grids. The .chk, .fchk, and .log files are included for all calculations. |
Technical Details | Calculations were performed in Gaussian16 |
EtCAAC5
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Description | All DFT calculations pertaining to CAAC5 with nitrogen bearing a diisopropylphenyl substituent and two ethyl groups on the quaternary carbon alpha to carbene center. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory with ultrafine integration grids. The .chk, .fchk, and .log files are included for all calculations. |
Technical Details | Calculations were performed in Gaussian09 |
EtCAAC6
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Description | All DFT calculations pertaining to CAAC6 with nitrogen bearing a diisopropylphenyl substituent and two ethyl groups on the quaternary carbon alpha to carbene center. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory with ultrafine integration grids. The .chk, .fchk, and .log files are included for all calculations. |
Technical Details | Calculations were performed in Gaussian09 |
EtPhBiCAAC
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Description | All DFT calculations pertaining to BiCAAC with nitrogen bearing a diisopropylphenyl substituent and a 1-phenylethyl group on the quaternary carbon alpha to carbene center. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory with ultrafine integration grids. The .chk, .fchk, and .log files are included for all calculations. |
Technical Details | Calculations were performed in Gaussian16 |
MePhCAAC5
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Description | All DFT calculations pertaining to CAAC5 with nitrogen bearing a diisopropylphenyl substituent and one methyl and one phenyl group on the quaternary carbon alpha to carbene center. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory with ultrafine integration grids. The .chk, .fchk, and .log files are included for all calculations. |
Technical Details | Calculations were performed in Gaussian16 |
MesNHC5
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Description | All DFT calculations pertaining to an NHC bearing a mesityl group on each nitrogen. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory with ultrafine integration grids. The .chk, .fchk, and .log files are included for all calculations. |
Technical Details | Calculations were performed in Gaussian16 |
SIMesNHC5
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Description | All DFT calculations pertaining to saturated NHC bearing a mesityl group on each nitrogen. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory with ultrafine integration grids. The .chk, .fchk, and .log files are included for all calculations. |
Technical Details | Calculations were performed in Gaussian16 |
- Collection
- Cite This Work
-
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
- Description
-
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.
- Creation Date
- 2020 to 2021
- Date Issued
- 2021
- Authors
- Principal Investigator
- Co Principal Investigators
- Funding
-
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.
- Topics
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- Language
- No linguistic content; Not applicable
- Identifier
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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
- Related Resources
- 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
- 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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