Synthesis of Arylpalladium(II) Boronates: Confirming the Structure and Chemical Competence of Pre-transmetalation Intermediates in the Suzuki-Miyaura Reaction.
Suzuki-Miyaura reaction
cross-coupling
palladium boronates
transmetalation
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
25 06 2021
25 06 2021
Historique:
received:
07
04
2021
pubmed:
24
4
2021
medline:
24
4
2021
entrez:
23
4
2021
Statut:
ppublish
Résumé
Palladium(II) boronates are recognized as fundamental pre-transmetalation intermediates in Suzuki-Miyaura cross-couplings. While these typically transient species have been detected and studied spectroscopically, it is conspicuous that they have never been isolated since this important reaction was discovered over forty years ago. This study reports the synthesis of a family of unprecedented arylpalladium(II) boronates that are, by design, kinetically stable at ambient temperature, both in solution and in the solid state. These properties enabled unambiguous crystallographic confirmation of their structure for the first time and their chemical competence in a Suzuki-Miyaura reaction was demonstrated.
Identifiants
pubmed: 33890395
doi: 10.1002/anie.202104802
doi:
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
14897-14901Informations de copyright
© 2021 Wiley-VCH GmbH.
Références
N. Miyaura, A. Suzuki, J. Chem. Soc. Chem. Commun. 1979, 866-867.
N. Miyaura, N. Yamada, A. Suzuki, Tetrahedron Lett. 1979, 20, 3437-3440.
A. J. J. Lennox, G. C. Lloyd-Jones, Chem. Soc. Rev. 2014, 43, 412-443.
J. P. G. Rygus, C. M. Crudden, J. Am. Chem. Soc. 2017, 139, 18124-18137.
A. Suzuki, Chem. Commun. 2005, 4759-4763.
I. Hussain, J. Capricho, M. A. Yawer, Adv. Synth. Catal. 2016, 358, 3320-3349.
J. S. Carey, D. Laffan, C. Thomson, M. T. Williams, Org. Biomol. Chem. 2006, 4, 2337-2347.
S. D. Roughley, A. M. Jordan, J. Med. Chem. 2011, 54, 3451-3479.
A. A. Thomas, H. Wang, A. F. Zahrt, S. E. Denmark, J. Am. Chem. Soc. 2017, 139, 3805-3821.
A. A. Thomas, S. E. Denmark, Science 2016, 352, 329-332.
A. A. Thomas, A. F. Zahrt, C. P. Delaney, S. E. Denmark, J. Am. Chem. Soc. 2018, 140, 4401-4416.
A. J. J. Lennox, G. C. Lloyd-Jones, Angew. Chem. Int. Ed. 2013, 52, 7362-7370;
Angew. Chem. 2013, 125, 7506-7515.
M. Butters, J. N. Harvey, J. Jover, A. J. J. Lennox, G. C. Lloyd-Jones, P. M. Murray, Angew. Chem. Int. Ed. 2010, 49, 5156-5160;
Angew. Chem. 2010, 122, 5282-5286.
M. A. Ortuño, A. Lledós, F. Maseras, G. Ujaque, ChemCatChem 2014, 6, 3132-3138.
B. P. Carrow, J. F. Hartwig, J. Am. Chem. Soc. 2011, 133, 2116-2119.
C. C. Ho, A. Olding, J. A. Smith, A. C. Bissember, Organometallics 2018, 37, 1745-1750.
S. E. Denmark, R. C. Smith, J. Am. Chem. Soc. 2010, 132, 1243-1245.
C. Zheng, B. F. Spielvogel, R. Y. Smith, N. S. Z. Hosmane, Z. Kristallogr. New Cryst. Struct. 2001, 216, 341-343.
H. Höpfl, V. Barba, G. Vargas, N. Farfan, R. Santillan, D. Castillo, Chem. Heterocycl. Compd. 1999, 35, 912-927.
I. J. Bruno, J. C. Cole, M. Kessler, J. Luo, W. D. S. Motherwell, L. H. Purkis, B. R. Smith, R. Taylor, R. I. Cooper, S. E. Harris, A. G. Orpen, J. Chem. Inf. Comput. Sci. 2004, 44, 2133-2144.
I. Pantcheva, Y. Nishihara, K. Osakada, Organometallics 2005, 24, 3815-3817.
P. Zhao, C. D. Incarvito, J. F. Hartwig, J. Am. Chem. Soc. 2007, 129, 1876-1877.
T. Maki, K. Ishihara, H. Yamamoto, Org. Lett. 2005, 7, 5043-5046.
We employed Density Functional Theory (DFT) to explore the transmetalation mechanism leading to biaryl 10 from a simpler analogue of structure 8 b′ (see Supporting Information). Computing the barrier from complex 8 b is particularly challenging, owing to uncertainties in energies associated with the modeling of water in the hydration step and complications that derive from the presence of the Bpin moiety within ligand 4 b.
We also demonstrated the capacity of complex 8 b to facilitate a SM reaction between 4-iodopyridine and 4-methoxyphenylboronic acid (see Supporting Information).