Thiourea-Catalyzed C-F Bond Activation: Amination of Benzylic Fluorides.
C−F activation
benzyl amines
benzyl fluorides
organocatalysis
thiourea
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
17 Aug 2020
17 Aug 2020
Historique:
received:
19
04
2020
pubmed:
22
4
2020
medline:
22
4
2020
entrez:
22
4
2020
Statut:
ppublish
Résumé
We describe the first thiourea-catalyzed C-F bond activation. The use of a thiourea catalyst and Ti(OiPr)
Identifiants
pubmed: 32315102
doi: 10.1002/chem.202001905
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
10620-10625Subventions
Organisme : Université de Bordeaux
Organisme : Centre National de la Recherche Scientifique
Organisme : Canadian Network for Research and Innovation in Machining Technology, Natural Sciences and Engineering Research Council of Canada
Organisme : FRQNT Network for Research on Protein Function, Engineering, and Applications
Organisme : Université Laval
Organisme : New Jersey Institute of Technology
Informations de copyright
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Références
S. J. Blanksby, G. B. Ellison, Acc. Chem. Res. 2003, 36, 255-263.
D. O′Hagan, Chem. Soc. Rev. 2008, 37, 308-319.
For a selection of reviews on C−F bond activation, see:
J. L. Kiplinger, T. G. Richmond, C. E. Osterberg, Chem. Rev. 1994, 94, 373-431;
H. Torrens, Coord. Chem. Rev. 2005, 249, 1957-1985;
H. Amii, K. Uneyama, Chem. Rev. 2009, 109, 2119-2183;
A. Nova, R. Mas-Ballesté, A. Lledós, Organometallics 2012, 31, 1245-1256;
M. F. Kuehnel, D. Lentz, R. Braun, Angew. Chem. Int. Ed. 2013, 52, 3328-3348;
Angew. Chem. 2013, 125, 3412-3433;
T. Stahl, H. F. T. Klare, M. Oestreich, ACS Catal. 2013, 3, 1578-1587;
T. Ahrens, J. Kohlmann, M. Ahrens, T. Braun, Chem. Rev. 2015, 115, 931-972;
T. A. Unzner, T. Magauer, Tetrahedron Lett. 2015, 56, 877-883;
Q. Shen, Y.-G. Huang, C. Liu, J.-C. Xiao, Q.-Y. Chen, Y. Guo, J. Fluorine Chem. 2015, 179, 14-22;
H. Yin, A. V. Zabula, E. J. Schelter, Dalton Trans. 2016, 45, 6313-6323;
W. Chen, C. Bakewell, M. R. Crimmin, Synthesis 2017, 49, 3165;
J.-D. Hamel, J.-F. Paquin, Chem. Commun. 2018, 54, 10224-10239;
T. Fujita, K. Fuchibe, J. Ichikawa, Angew. Chem. Int. Ed. 2019, 58, 390-402;
Angew. Chem. 2019, 131, 396-408.
For reviews on organofluorine compounds as hydrogen-bond acceptors, see:
H.-J. Schneider, Chem. Sci. 2012, 3, 1381-1394;
P. A. Champagne, J. Desroches, J.-F. Paquin, Synthesis 2015, 47, 306-322.
P. A. Champagne, J. Pomarole, M.-È. Thérien, Y. Benhassine, S. Beaulieu, C. Y. Legault, J.-F. Paquin, Org. Lett. 2013, 15, 2210-2213.
P. A. Champagne, A. Saint-Martin, M. Drouin, J.-F. Paquin, Beilstein J. Org. Chem. 2013, 9, 2451-2456.
P. A. Champagne, M. Drouin, C. Y. Legault, C. Audubert, J.-F. Paquin, J. Fluorine Chem. 2015, 171, 113-119.
N. S. Keddie, P. A. Champagne, J. Desroches, J.-F. Paquin, D. O'Hagan, Beilstein J. Org. Chem. 2018, 14, 106-113.
P. A. Champagne, Y. Benhassine, J. Desroches, J.-F. Paquin, Angew. Chem. Int. Ed. 2014, 53, 13835-13839;
Angew. Chem. 2014, 126, 14055-14059.
For related reaction on propargylic fluoride, see: J.-D. Hamel, M. Beaudoin, M. Cloutier, J.-F. Paquin, Synlett 2017, 28, 2823-2828.
R. Hemelaere, P. A. Champagne, J. Desroches, J.-F. Paquin, J. Fluorine Chem. 2016, 190, 1-6.
M. Dryzhakov, J. Moran, ACS Catal. 2016, 6, 3670-3673;
M. Dryzhakov, E. Richmond, G. Li, J. Moran, J. Fluorine Chem. 2017, 193, 45-51.
T. Okino, Y. Hoashi, Y. Takemoto, J. Am. Chem. Soc. 2003, 125, 12672-12673;
Y. Hoashi, T. Okino, Y. Takemoto, Angew. Chem. Int. Ed. 2005, 44, 4032-4035;
Angew. Chem. 2005, 117, 4100-4103;
T. Okino, Y. Hoashi, T. Furukawa, X. Xu, Y. Takemoto, J. Am. Chem. Soc. 2005, 127, 119-125.
P. R. Schreiner, Chem. Soc. Rev. 2003, 32, 289-296;
Y. Takemoto, Org. Biomol. Chem. 2005, 3, 4299-4306;
M. S. Taylor, E. N. Jacobsen, Angew. Chem. Int. Ed. 2006, 45, 1520-1543;
Angew. Chem. 2006, 118, 1550-1573;
S. Koeller, J. Kadota, A. Deffieux, F. Peruch, S. Massip, J.-M. Léger, J.-P. Desvergne, B. Bibal, J. Am. Chem. Soc. 2009, 131, 15088-15089;
O. V. Serdyuk, C. M. Heckel, S. B. Tsogoeva, Org. Biomol. Chem. 2013, 11, 7051-7071;
C. Thomas, B. Bibal, Green Chem. 2014, 16, 1687-1699.
Reactions performed with nonpolar hexane as the solvent consistently afforded higher conversion than those with the more polar dichloromethane. These solvents were chosen because neither is a hydrogen-bond acceptor, and while hexane is not hydrogen-bond donor, CH2Cl2 is a very weak one, see:
P. M. E. Mancini, A. Terenzani, C. Adam, L. R. Vottero, J. Phys. Org. Chem. 1997, 10, 849-860.
K. M. Lippert, K. Hof, D. Gerbig, D. Ley, H. Hausmann, S. Guenther, P. R. Schreiner, Eur. J. Org. Chem. 2012, 5919-5927.
For selected examples of known fluoride sensors based on thiourea, see:
M. Vázquez, L. Fabbrizzi, A. Taglietti, R. M. Pedrido, A. M. Gonzalez-Noya, M. R. Bermejo, Angew. Chem. Int. Ed. 2004, 43, 1962-1965;
Angew. Chem. 2004, 116, 1996-1999;
M. Boiocchi, L. Del Boca, D. Esteban Gomez, L. Fabbrizzi, M. Licchelli, E. Monzani, J. Am. Chem. Soc. 2004, 126, 16507-16514;
Z. Zhang, P. R. Schreiner, Chem. Soc. Rev. 2009, 38, 1187-1198;
J. Kang, Y. J. Lee, S. K. Lee, J. H. Lee, J. J. Park, Y. Kim, S.-J. Kim, C. Kim, Supramol. Chem. 2010, 22, 267-273;
P. Bose, P. Ghosh, Chem. Commun. 2010, 46, 2962-2964;
J. Krishnamurthi, T. Ono, S. Amemori, H. Komatsu, S. Shinkai, K. Sada, Chem. Commun. 2011, 47, 1571-1573;
V. Amendola, G. Bergamaschi, M. Boiocchi, L. Fabbrizzi, L. Mosca, J. Am. Chem. Soc. 2013, 135, 6345-6355;
S. Koeller, M.-H. Lescure, C. Davies, J.-P. Desvergne, S. Massip, B. Bibal, Eur. J. Org. Chem. 2017, 5627-5631.
Y. R. Luo, Comprehensive Handbook of Chemical Bond Energies, CRC Press, Boca Raton, 2007.
For a review on the preparation and applications of titanium fluoride complexes, see: G. B. Nikiforov, H. W. Roesky, D. Koley, Coord. Chem. Rev. 2014, 258-259, 16-57.
Gaussian 16, Revision A.03, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, D. J. Fox, Gaussian, Inc., Wallingford CT, 2016.
G. Luchini, D. M. H. Ascough, J. V. Alegre-Requena, V. Gouverneur, R. S. Paton, Tetrahedron 2019, 75, 697-702.
See the Supporting Information for details.
M. O. Sinnokrot, C. D. Sherrill, J. Phys. Chem. A 2006, 110, 10656-10668.
Binding of morpholine to 2 g was also investigated computationally. Similar to BnF, the binding is endergonic (ΔG=+3.8 kcal mol−1) and as such, we do not anticipate that the amine nucleophile or the benzylic amine product interfere with the catalytic cycle shown in Figure 2.
A reaction half-life of 24.8 h is calculated using the Eyring equation.
The fluoride ion could also react with the glassware, see: M. M. Nielsen, Y. Qiao, Y. Wang, C. M. Pedersen, Eur. J. Org. Chem. 2020, 140-144.