[en] Herein, we report a photocatalytic procedure that enables the acylation/arylation of unfunctionalized alkyl derivatives in flow. The method exploits the ability of the decatungstate anion to act as a hydrogen atom abstractor and produce nucleophilic carbon-centered radicals that are intercepted by a nickel catalyst to ultimately forge C(sp3 )-C(sp2 ) bonds. Owing to the intensified conditions in flow, the reaction time can be reduced from 12-48 hours to only 5-15 minutes. Finally, kinetic measurements highlight how the intensified conditions do not change the reaction mechanism but reliably speed up the overall process.
Disciplines :
Chemistry
Author, co-author :
Mazzarella, Daniele ; Flow Chemistry Group, Van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands
Pulcinella, Antonio ; Flow Chemistry Group, Van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands
Bovy, Loïc ; Université de Liège - ULiège > Département de chimie (sciences) > Synthèse organique appliquée ; Flow Chemistry Group, Van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands
Broersma, Rémy; Signify Research, High Tech Campus 7, 5656, AE, Eindhoven, The Netherlands
Noël, Timothy ; Flow Chemistry Group, Van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands
Language :
English
Title :
Rapid and Direct Photocatalytic C(sp3 )-H Acylation and Arylation in Flow.
A.P. and T.N. have received funding from the European Union H2020 research and innovation program under the Marie S. Curie Grant Agreement No 860762 (CHAIR). L.B. has received financial support from the European Union H2020 Erasmus+ program (OU201761).
R. C. McAtee, E. J. McClain, C. R. J. Stephenson, Trends Chem. 2019, 1, 111–125.
G. E. M. Crisenza, P. Melchiorre, Nat. Commun. 2020, 11, 803;
J. K. Matsui, S. B. Lang, D. R. Heitz, G. A. Molander, ACS Catal. 2017, 7, 2563–2575.
For selected reviews on the topic, see:
P. G. Cozzi, A. Gualandi, M. Anselmi, F. Calogero, S. Potenti, E. Bassan, P. Ceroni, Org. Biomol. Chem. 2021, 19, 3527–3550;
M. De Abreu, P. Belmont, E. Brachet, Eur. J. Org. Chem. 2020, 1327–1378;
J. Twilton, C. Le, P. Zhang, M. H. Shaw, R. W. Evans, D. W. C. MacMillan, Nat. Rev. Chem. 2017, 1, 0052;
C. K. Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev. 2013, 113, 5322–5363.
For selected examples:
N. Alandini, L. Buzzetti, G. Favi, T. Schulte, L. Candish, K. D. Collins, P. Melchiorre, Angew. Chem. Int. Ed. 2020, 59, 5248–5253;
Angew. Chem. 2020, 132, 5286–5291;
E. M. Dauncey, S. U. Dighe, J. J. Douglas, D. Leonori, Chem. Sci. 2019, 10, 7728–7733;
H.-H. Zhang, J.-J. Zhao, S. Yu, J. Am. Chem. Soc. 2018, 140, 16914–16919;
L. Guo, F. Song, S. Zhu, H. Li, L. Chu, Nat. Commun. 2018, 9, 4543;
J. A. Kautzky, T. Wang, R. W. Evans, D. W. C. MacMillan, J. Am. Chem. Soc. 2018, 140, 6522–6526;
S. M. Thullen, T. Rovis, J. Am. Chem. Soc. 2017, 139, 15504–15508;
M. Jouffroy, D. N. Primer, G. A. Molander, J. Am. Chem. Soc. 2016, 138, 475–478;
X.-Z. Shu, M. Zhang, Y. He, H. Frei, F. D. Toste, J. Am. Chem. Soc. 2014, 136, 5844–5847;
Z. Zuo, D. T. Ahneman, L. Chu, J. A. Terrett, A. G. Doyle, D. W. C. MacMillan, Science 2014, 345, 437–440;
J. C. Tellis, D. N. Primer, G. A. Molander, Science 2014, 345, 433–436.
S. Govaerts, A. Nyuchev, T. Noël, J. Flow Chem. 2020, 10, 13–71;
L. Capaldo, L. L. Quadri, D. Ravelli, Green Chem. 2020, 22, 3376–3396;
L. Capaldo, D. Ravelli, Eur. J. Org. Chem. 2017, 2056–2071.
For a review on the topic, see:
W.-J. Zhou, Y.-H. Zhang, Y.-Y. Gui, L. Sun, D.-G. Yu, Synthesis 2018, 50, 3359–3378; For specific examples on HAT metallaphotoredox:
P. J. Sarver, V. Bacauanu, D. M. Schultz, D. A. DiRocco, Y.-H. Lam, E. C. Sherer, D. W. C. MacMillan, Nat. Chem. 2020, 12, 459–467;
L. Wang, T. Wang, G.-J. Cheng, X. Li, J.-J. Wei, B. Guo, C. Zheng, G. Chen, C. Ran, C. Zheng, ACS Catal. 2020, 10, 7543–7551;
I. B. Perry, T. F. Brewer, P. J. Sarver, D. M. Schultz, D. A. DiRocco, D. W. C. MacMillan, Nature 2018, 560, 70–75;
Y. Shen, Y. Gu, R. Martin, J. Am. Chem. Soc. 2018, 140, 12200–12209;
H. Cao, Y. Kuang, X. Shi, K. L. Wong, B. B. Tan, J. M. C. Kwan, X. Liu, J. Wu, Nat. Commun. 2020, 11, 1956.
For systems using a HAT reagent generated through photoredox catalysis:
J. D. Cuthbertson, D. W. C. MacMillan, Nature 2015, 519, 74–77;
M. H. Shaw, V. W. Shurtleff, J. A. Terrett, J. D. Cuthbertson, D. W. C. MacMillan, Science 2016, 352, 1304–1308;
X. Zhang, D. W. C. MacMillan, J. Am. Chem. Soc. 2017, 139, 11353–11356; For systems involving the generation of chlorine atom as the HAT reagent through photolysis of the nickel catalyst:
S. K. Kariofillis, B. J. Shields, M. A. Tekle-Smith, M. J. Zacuto, A. G. Doyle, J. Am. Chem. Soc. 2020, 142, 7683–7689;
L. K. G. Ackerman, J. I. Martinez Alvarado, A. G. Doyle, J. Am. Chem. Soc. 2018, 140, 14059–14063;
M. K. Nielsen, B. J. Shields, J. Liu, M. J. Williams, M. J. Zacuto, A. G. Doyle, Angew. Chem. Int. Ed. 2017, 56, 7191–7194;
Angew. Chem. 2017, 129, 7297–7300;
B. J. Shields, A. G. Doyle, J. Am. Chem. Soc. 2016, 138, 12719–12722.
For a paper studying the kinetics of HAT with DT: I. N. Lykakis, C. Tanielian, R. Seghrouchni, M. Orfanopoulos, J. Mol. Catal. A Chem. 2007, 262, 176–184.
T. Wan, L. Capaldo, G. Laudadio, A. V. Nyuchev, J. A. Rincón, P. García-Losada, C. Mateos, M. O. Frederick, M. Nuño, T. Noël, Angew. Chem. Int. Ed. 2021, 60, 17893–17897;
Angew. Chem. 2021, 133, 18037–18041;
Z. Wen, A. Maheshwari, C. Sambiagio, Y. Deng, G. Laudadio, K. van Aken, Y. Sun, H. P. L. Gemoets, T. Noël, Org. Process Res. Dev. 2020, 24, 2356–2361;
G. Laudadio, Y. Deng, K. van der Wal, D. Ravelli, M. Nuño, M. Fagnoni, D. Guthrie, Y. Sun, T. Noël, Science 2020, 369, 92–96;
G. Laudadio, S. Govaerts, Y. Wang, D. Ravelli, H. Koolman, M. Fagnoni, S. Djuric, T. Noël, Angew. Chem. Int. Ed. 2018, 57, 4078–4082;
Angew. Chem. 2018, 130, 4142–4146.
D. Ravelli, M. Fagnoni, T. Fukuyama, T. Nishikawa, I. Ryu, ACS Catal. 2018, 8, 701–713.
B. Fletcher, N. K. Suleman, J. M. Tanko, J. Am. Chem. Soc. 1998, 120, 11839–11844;
D. F. Banks, E. S. Huyser, J. Kleinberg, J. Org. Chem. 1964, 29, 3692–3693;
M. S. Kharasch, M. G. Berkman, J. Org. Chem. 1941, 6, 810–817;
D. D. Tanner, M. W. Mosher, N. J. Bunce, Can. J. Chem. 1969, 47, 4809–4811;
H. Matsubara, Y. Hino, M. Tokizane, I. Ryu, Chem. Eng. J. 2011, 167, 567–571.
For selected photochemical systems using chlorine radical in HAT processes see:
S. Rohe, A. O. Morris, T. McCallum, L. Barriault, Angew. Chem. Int. Ed. 2018, 57, 15664–15669;
Angew. Chem. 2018, 130, 15890–15895;
Q. Yang, Y.-H. Wang, Y. Qiao, M. Gau, P. J. Carroll, P. J. Walsh, E. J. Schelter, Science 2021, 372, 847–852.
D. Cambié, C. Bottecchia, N. J. W. Straathof, V. Hessel, T. Noël, Chem. Rev. 2016, 116, 10276–10341.
Z. G. Brill, C. B. Ritts, U. F. Mansoor, N. Sciammetta, Org. Lett. 2020, 22, 410–416;
W. Debrouwer, W. Kimpe, R. Dangreau, K. Huvaere, H. P. L. Gemoets, M. Mottaghi, S. Kuhn, K. Van Aken, Org. Process Res. Dev. 2020, 24, 2319–2325.
For a pertinent study over the effect of light intensity on photoreactions: T. D. Svejstrup, A. Chatterjee, D. Shekin, T. Wagner, J. Zach, M. J. Johansson, G. Bergonzini, B. König, ChemPhotoChem 2021, https://doi.org/10.1002/cptc.202100059.
For electron-rich aryl bromides, we have observed the formation of nickel black at the end of the reaction, which possibly affects the overall efficiency. For a similar issue, see: S. Gisbertz, S. Reischauer, B. Pieber, Nat. Catal. 2020, 3, 611–620.
E. M. Simmons, J. F. Hartwig, Angew. Chem. Int. Ed. 2012, 51, 3066–3072;