Copper(I) Photocatalyzed Bromonitroalkylation of Olefins: Evidence for Highly Efficient Inner-Sphere Pathways.
Copper
Homogeneous Catalysis
Photocatalysis
Radicals
Reaction Mechanism
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:
11 Apr 2023
11 Apr 2023
Historique:
received:
25
12
2022
medline:
3
2
2023
pubmed:
3
2
2023
entrez:
2
2
2023
Statut:
ppublish
Résumé
We report the visible light-mediated copper-catalyzed vicinal difunctionalization of olefins utilizing bromonitroalkanes as ATRA reagents. This protocol is characterized by high yields and fast reaction times under environmentally benign reaction conditions with exceptional scope, allowing the rapid functionalization of both activated and unactivated olefins. Moreover, late-stage functionnalization of biologically active molecules and upscaling to gram quantities is demonstrated, which offers manifold possibilities for further transformations, e.g. access to nitro- and aminocyclopropanes. Besides the synthetic utility of the title transformation, this study undergirds the exclusive role of copper in photoredox catalysis showing its ability to stabilize and interact with radical intermediates in its coordination sphere. EPR studies suggest that such interactions can even outperform a highly favorable cyclization of transient to persistent radicals contrasting iridium-based photocatalysts.
Identifiants
pubmed: 36732299
doi: 10.1002/anie.202219086
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202219086Subventions
Organisme : DFG
ID : TRR 325444632635-A1
Organisme : DFG
ID : RE3630/5
Organisme : Fonds der Chemischen Industrie
ID : Ph.D. fellowship
Organisme : Deutsche Forschungsgemeinschaft
ID : RE 948/18
Informations de copyright
© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
Références
M. S. Kharasch, E. V. Jensen, W. H. Urry, Science 1945, 102, 128;
M. S. Kharasch, W. H. Urry, E. V. Jensen, J. Am. Chem. Soc. 1945, 67, 1626;
M. S. Kharasch, P. S. Skell, P. Fisher, J. Am. Chem. Soc. 1948, 70, 1055.
M. H. Shaw, J. Twilton, D. W. C. MacMillan, J. Org. Chem. 2016, 81, 6898.
T. Courant, G. Masson, J. Org. Chem. 2016, 81, 6945.
A. Hossain, A. Bhattacharyya, O. Reiser, Science 2019, 364, aav9713.
S. Engl, O. Reiser, Chem. Soc. Rev. 2022, 51, 5287.
H. Cao, S. Ma, Y. Feng, Y. Guo, P. Jiao, Chem. Commun. 2022, 58, 1780;
G. Hirata, T. Shimada, T. Nishikata, Org. Lett. 2020, 22, 8952;
M. Iwasaki, Y. Ikemoto, Y. Nishihara, Org. Lett. 2020, 22, 7577.
Y. Tsuchiya, R. Onai, D. Uraguchi, T. Ooi, Chem. Commun. 2020, 56, 11014.
S. Engl, O. Reiser, Eur. J. Org. Chem. 2020, 1523;
C. K. Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev. 2013, 113, 5322.
M. P. Thorpe, A. N. Smith, M. S. Crocker, J. N. Johnston, J. Org. Chem. 2022, 87, 5451-5455.
A. Hossain, S. Engl, E. Lutsker, O. Reiser, ACS Catal. 2019, 9, 1103.
C. Minozzi, A. Caron, J.-C. Grenier-Petel, J. Santandrea, S. K. Collins, Angew. Chem. Int. Ed. 2018, 57, 5477;
Angew. Chem. 2018, 130, 5575.
S. Engl, O. Reiser, ACS Catal. 2020, 10, 9899.
S. Paria, M. Pirtsch, V. Kais, O. Reiser, Synthesis 2013, 45, 2689.
X.-J. Tang, W. R. Dolbier, Angew. Chem. Int. Ed. 2015, 54, 4246;
Angew. Chem. 2015, 127, 4320.
T. Akasaka, S. Kurosaka, Y. Uchida, M. Tanaka, K. Sato, I. Hayakawa, Antimicrob. Agents Chemother. 1998, 42, 1284;
S. Kawamura, Y. Unno, A. List, A. Mizuno, M. Tanaka, T. Sasaki, M. Arisawa, A. Asai, M. Groll, S. Shuto, J. Med. Chem. 2013, 56, 3689;
H.-L. Teng, Y. Luo, B. Wang, L. Zhang, M. Nishiura, Z. Hou, Angew. Chem. Int. Ed. 2016, 55, 15406;
Angew. Chem. 2016, 128, 15632.
K. G. Hugentobler, H. Sharif, M. Rasparini, R. S. Heath, N. J. Turner, Org. Biomol. Chem. 2016, 14, 8064.
M. Rasparini, M. Taddei, E. Cini, C. Minelli, N. Turner, K. G. Hugentobler, Rasparini, Marcello; Taddei, Maurizio; Cini, Elena; Minelli, Cosima; Turner, Nicholas; Hugentobler, Katharina, A1 2013-05-08, 2013.
S. Tanaka, S. Kohmoto, M. Yamamoto, K. Yamada, Nippon Shokuhin Kagaku Kogaku Kaishi 1989, 1742.
B. Moreau, D. Alberico, V. N. Lindsay, A. B. Charette, Tetrahedron 2012, 68, 3487.
N. Hoang, X. Zhang, C. Zhang, V. Vo, F. Leng, L. Saxena, F. Yin, F. Lu, G. Zheng, P. Bhowmik, et al., Bioorg. Med. Chem. 2018, 26, 1523.
S. Ulrich, R. Ricken, M. Adli, Eur. Neuropsychopharmacol. 2017, 27, 697.
J. E. T. Corrie, B. C. Gilbert, V. R. N. Munasinghe, A. C. Whitwood, J. Chem. Soc. Perkin Trans. 2 2000, 2483.
Deposition numbers 2192294 (4 h) and 2192295 (9) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service.
L. M. Huffman, S. S. Stahl, J. Am. Chem. Soc. 2008, 130, 9196.
A. E. King, L. M. Huffman, A. Casitas, M. Costas, X. Ribas, S. S. Stahl, J. Am. Chem. Soc. 2010, 132, 12068.
L. M. Huffman, A. Casitas, M. Font, M. Canta, M. Costas, X. Ribas, S. S. Stahl, Chem. Eur. J. 2011, 17, 10643.