10.1002/anie.202105895
Angewandte Chemie International Edition
RESEARCH ARTICLE
17510; Angew. Chem. 2019, 131, 17670-17672; d) Y. Yu, P. Guo,
J.-S. Zhong, Y. Yuan, K.-Y. Ye, Org. Chem. Front. 2020, 7, 131-
135.
Acknowledgements
J.P.B. and X.T. thank the Alexander von Humboldt Foundation for
funding, provided within the framework of the Sofja Kovalevskaja
Award endowed by the German Federal Ministry of Education and
Research. We thank Regina Hoheisel for support in
spectroelectrochemistry. We thank Prof. Patrick Nürnberger,
Sebastian Bergwinkl, Stephan Muth, Prof. Robert Wolf and Julia
Märsch for assisting with glovebox preparations and FT-IR
measurements. We thank Prof. John C. Walton for discussions
on EPR spectroscopy. T.K. thanks the Deutsche Bundestiftung
Umwelt (DBU) for a graduate scholarship. S.Y. is grateful for
funding provided by a DAAD scholarship and thanks the SynCat
programme of the Elite Network of Bavaria. R.dV-R. and S.R.
acknowledge funding by the German Research Foundation
(DFG) under Germany’s excellence strategy EXC 2089/1 –
390776260. S.R. thanks the International Max Planck Research
School on Advanced Photon Science (IMPRS-APS).
[5]
For recent examples on homogeneous photoelectrochemistry, see:
a) S. Wu, J. Žurauskas, M. Domański, P. S. Hitzfeld, V. Butera, D.
J. Scott, J. Rehbein, A. Kumar, E. Thyrhaug, J. Hauer, J. P.
Barham, Org. Chem. Front. 2021, 8, 1132-1142; b) P. Xu, P.-Y.
Chen, H.-C. Xu, Angew. Chem. Int. Ed. 2020, 59, 14275-14280;
Angew. Chem. 2020, 132, 14381-14386; c) X.-L. Lai, X.-M. Shu,
J. Song, H.-C. Xu, Angew. Chem. Int. Ed. 2020, 59, 10626-10632;
Angew. Chem. 2020, 132, 10713-10719; d) L. Niu, C. Jiang, Y.
Liang, D. Liu, F. Bu, R. Shi, H. Chen, A. D. Chowdhury, A. Lei,
J. Am. Chem. Soc. 2020, 142, 17693-17702; e) Y. Qiu, A.
Scheremetjew, L. H. Finger, L. Ackermann, Chem. Eur. J. 2020,
26, 3241-3246; f) N. G. W. Cowper, C. P. Chernowsky, O. P.
Williams, Z. K. Wickens, J. Am. Chem. Soc. 2020, 142, 2093-
2099; g) H. Huang, Z. M. Strater, T. H. Lambert, J. Am. Chem.
Soc. 2020, 142, 1698-1703; h) H. Kim, H. Kim, T. H. Lambert, S.
Lin, J. Am. Chem. Soc. 2020, 142, 2087-2092; i) H. Huang, T. H.
Lambert, Angew. Chem. Int. Ed. 2020, 59, 658-662; Angew. Chem.
2020, 132, 668-672; j) W. Zhang, K. L. Carpenter, S. Lin, Angew.
Chem. Int. Ed. 2020, 59, 409-417; Angew. Chem. 2020, 132, 417-
425; k) H. Huang, Z. M. Strater, M. Rauch, J. Shee, T. J. Sisto, C.
Nuckolls, T. H. Lambert, Angew. Chem. Int. Ed. 2019, 58, 13318-
13322; Angew. Chem. 2019, 131, 13452-13456; l) J. H. Wang, X.
B. Li, J. Li, T. Lei, H. L. Wu, X. L. Nan, C. H. Tung, L. Z. Wu,
Chem. Commun. 2019, 55, 10376-10379; m) L. Zhang, L. Liardet,
J. Luo, D. Ren, M. Grätzel, X. Hu, Nat. Catal. 2019, 2, 366-373;
n) F. Wang, S. S. Stahl, Angew. Chem. Int. Ed. 2019, 58, 6385-
6390; Angew. Chem. 2019, 131, 6451-6456; o) H. Yan, Z. W. Hou,
H.-C. Xu, Angew. Chem. Int. Ed. 2019, 58, 4592-4595; Angew.
Chem. 2019, 131, 4640-4643.
Keywords: photoelectrochemistry • olefination • deoxygenation •
radical anion • preassembly
[1]
Selected reviews on photochemistry: a) Q.-Q. Zhou, Y.-Q. Zou,
L.-Q. Lu, W.-J. Xiao, Angew. Chem. Int. Ed. 2019, 58, 1586-1604;
Angew. Chem. 2019, 131, 1600-1619; b) L. Marzo, S. K. Pagire,
O. Reiser, B. König, Angew. Chem. Int. Ed. 2018, 57, 10034-
10072; Angew. Chem. 2018, 130, 10188-10228; c) J. Xie, H. Jin,
A. S. K. Hashmi, Chem. Soc. Rev. 2017, 46, 5193-5203; d) N. A.
Romero, D. A. Nicewicz, Chem. Rev. 2016, 116, 10075-10166; e)
C. K. Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev. 2013,
113, 5322-5363.
[6]
[7]
L. Pause, M. Robert, J.-M. Savéant, J. Am. Chem. Soc.1999, 121,
7158-7159.
For reductions of benzyl radicals to benzyl anions by PRC: a) K.
Donabauer, B. König, Acc. Chem. Res. 2021, 54, 242-252. For
examples of electrochemical reports: b) W. Zhang, S. Lin, J. Am.
Chem. Soc. 2020, 142, 20661-20670; c) L. Lu, J. C. Siu, Y. Lai,
S. Lin, J. Am. Chem. Soc. 2020, 142, 21272-21278. For the
reduction potential of
a benzyl radical: d) J. Grimshaw,
[2]
[3]
Selected general reviews on electrochemistry: a) T. H. Meyer, I.
Choi, C. Tian, L. Ackermann, Chem, 2020, 6, 2484-2496; b) P.
Xiong, H.-C. Xu, Acc. Chem. Res. 2019, 52, 3339-3350; c) S.
Tang, Y. Liu, A. Lei, Chem. 2018, 4, 27-45; d) A. Wiebe, T.
Gieshoff, S. Möhle, E. Rodrigo, M. Zirbes, S. R. Waldvogel,
Angew. Chem. Int. Ed. 2018, 57, 5594-5619; Angew. Chem. 2018,
130, 5694-5721; e) M. Yan, Y. Kawamata, P. S. Baran, Chem. Rev.
2017, 117, 13230-13319.
For selected representative examples, see: a) K. Targos, O. P.
Williams, Z. Wickens, J. Am. Chem. Soc. 2021, 143, 4125-4132;
b) D. Rombach, H.-A. Wagenknecht, Angew. Chem. Int. Ed. 2019,
59, 300-303; Angew. Chem. Int. Ed. 2019, 132, 306-310; c) J. I.
Bardagi, I. Ghosh, M. Schmalzbauer, T. Ghosh, B. König, Eur. J.
Org. Chem. 2018, 34-40; d) M. Neumeier, D. Sampedro, M.
Májek, V. A. de la Peña O'Shea, A. Jacobi von Wangelin, R.
Pérez-Ruiz, Chem. Eur. J. 2018, 24, 105-108; e) L. Zeng, T. Liu,
C. He, D. Shi, F. Zhang, C. Duan, J. Am. Chem. Soc. 2016, 138,
3958-3961; f) I. Ghosh, B. König, Angew. Chem. Int. Ed. 2016,
55, 7676-7679; Angew. Chem. 2016, 128, 7806-7810; g) I. Ghosh,
T. Ghosh, J. I. Bardagi, B. König, Science 2014, 346, 725-728; h)
H. Li, X. Tang, J. H. Pang, X. Wu, E. K. L. Yeow, J. Wu, S. Chiba,
J. Am. Chem. Soc. 2021, 143, 481-487. For full reviews, see: i) F.
Glaser, C. Kerzig, O. S. Wenger, Angew. Chem. Int. Ed. 2020, 59,
10266-10284; Angew. Chem. 2020, 132, 10350-10370; j) M.
Schmalzbauer, M. Marcon, B. König, Angew. Chem. Int. Ed. 2020,
60, 6270-6292; Angew. Chem. 2020, 133, 6338-6363.
Electrochemical Reactions and Mechanisms in Organic
Chemistry, Elsevier 2000, pp. 89-157.
The alkane product likely forms via high-voltage-mediated C=C
bond reduction, see: X. Liu, R. Liu, J. Qiu, X. Cheng, G. Li,
Angew. Chem. Int. Ed. 2020, 59, 13962-13967; Angew. Chem.
2020, 132, 14066-14071.
For reviews on photosensitized TTET isomerizations of alkenes
and its use in tandem strategies: a) J. J. Molloy, T. Morack, R.
Gilmour, Angew. Chem. Int. Ed. 2019, 58, 13654-13664; Angew.
Chem. 2019, 131, 13789-13800; b) S. Yakubov, J. P. Barham,
Beilstein J. Org. Chem. 2020, 16, 2151-2192; c) D. C. Fabry, M.
A. Ronge, M. Rueping, Chem.-Eur. J. 2014, 21, 5350-5354; d) J.
J. Molloy, M. Schäfer, M. Wienhold, T. Morack, C. D. Daniliuc,
R. Gilmour, Science 2020, 369, 302-306.
We found that although RVC (foam) electrodes provided a large
surface area to the reaction and were superior to graphite felt,
mechanical shearing oftentimes occurred. Fe plate was more
robust and gave a similar yield of 2a (see SI).
For reviews on electrode materials in organic electrochemistry: a)
A. M. Couper, D. Pletcher, F. C. Walsh, Chem. Rev. 1990, 90, 857-
865; b) D. M. Heard, A. J. J. Lennox, Angew. Chem. Int. Ed. 2020,
59, 18866-18884; Angew. Chem. 2020, 132, 19026-19044.
a) J. Iqbal, R. R. Srivastava, J. Org. Chem. 1992, 57, 2001-2007;
b) H. A. Dabbagh, M. Zamani, Appl. Catal. A. 2011, 404, 141-
148. A method for selective elimination to form terminal olefins
was reported but requires triphosgene: Org. Lett. 2019, 21, 5611-
5615.
S. Jin, H. T. Dang, G. C. Haug, R. He, V. D. Nguyen, V. T. Nguyen,
H. D. Arman, K. S. Schanze, O. V. Larianov, J. Am. Chem. Soc.
2020, 142, 1603-1613.
J. P. Cole, D.-F. Chen, M. Kudisch, R. M. Pearson, C.-H. Lim, G.
M. Miyake, J. Am. Chem. Soc. 2020, 142, 13573-13581.
[8]
[9]
[10]
[11]
[12]
[4]
For a full review on the combination of photoredox catalysis and
organic electrochemistry: a) J. P. Barham, B. König, Angew.
Chem. Int. Ed. 2020, 59, 11732-11747; Angew. Chem. 2020, 132,
11828-11844. For highlights on this topic: b) J. Liu, L. Lu, D.
Wood, S. Lin, ACS Cent. Sci. 2020, 6, 1317-1340; c) L. Capaldo,
L. L. Quadri, D. Ravelli, Angew. Chem. Int. Ed. 2019, 58, 17508-
[13]
[14]
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