10.1002/anie.202000146
Angewandte Chemie International Edition
COMMUNICATION
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Lu, L.-W. Ye, J. Am. Chem. Soc. 2015, 137, 9567; h) A. Prechter,
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Cremonesi, L. Dumitrescu, Angew. Chem. Int. Ed. 2011, 50, 8931;
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Chem. Int. Ed. 2011, 50, 7354; Angew. Chem. 2011, 123, 7492.
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Selected examples: a) D. Hernández-Guerra, A. Hlavačková, C.
Pramthaisong, I. Vespoli, R. Pohl, T. Slanina, U. Jahn, Angew.
Chem. Int. Ed. 2019, 58, 12440; Angew. Chem. 2019, 131, 12570;
b) A. Bakhoda, Q. Jiang, Y. M. Badiei, J. A. Bertke, T. R. Cundari,
T. H. Warren, Angew. Chem. Int. Ed. 2019, 58, 3421; Angew.
Chem. 2019, 131, 3459; c) K.-P. Shing, Y. Liu, B. Cao, X.-Y.
Chang, T. You, C.-M. Che, Angew. Chem. Int. Ed. 2018, 57, 11947;
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Ghosha, B. König, Chem. Sci. 2015, 6, 987; e) E. P. Farney, T. P.
Yoon, Angew. Chem. Int. Ed. 2014, 53, 793; Angew. Chem. 2014,
126, 812; f) Nguyen, K. Sun, T. G. Driver, J. Am. Chem. Soc. 2012,
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azide 4a only delivered 3a in lower than 30% yield with a low
conversion, demonstrating that sulfilimine 2a is more reactive
than azide 4a.
With monodeuterated substrate 1a-D, two isotope experiments
by employing were conducted to understand the kinetic isotope
effects of both the photoreaction and the rhodium-catalyzed
transformation (Scheme 3). Same primary isotope effects of
1.63:1 were observed,[19] indicating that these two processes
have a similar rate-determining step, for example, a C−H insertion
or a hydrogen atom migration.
[3]
[4]
H / D
H / D
H / D
photolysis
Martin's Sulfurane
Et2O, N2, rt
or rhodium catalysis
N
N
H
NH2
S
Ph
Ph
1a-D
3a-D
2a-D
with photolysis:
with rhodium catalysis:
k
H / kD = 1.63
H / kD = 1.63
k
Scheme 3. Isotope experiments.
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Selected examples: a) C. G. Espino, J. Du Bois, Angew. Chem.
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In conclusion, we have described aryl sulfilimines as a new
generation of nitrene precursors for the synthesis of carbazoles
and related heterocycles by means of either visible light-
irradiation or rhodium catalysis. A straightforward comparison
with the commonly employed azides indicated that sulfilimines are
more reactive substrates, rendering its synthetic use under milder
reaction conditions. Furthermore, sulfide as a safe and readily
removable leaving group makes this method a promising
alternative for carbazole synthesis. The gram scale synthesis of
Clausine C was efficiently performed with a simple purification
step, demonstrating the distinct applicability and scalability of the
current reaction.
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[7]
Selected examples: a) D. F. Taber, W. Tian, J. Am. Chem. Soc.
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Selected examples: a) H. Jung, M. Schrader, D. Kim, M.-H. Baik,
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Hwang, Y. Park, Y. B. Kim, D. Kim, S. Chang, Angew. Chem. Int.
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2013, 2, 466; b) H.-J. Knölker, K. R. Reddy, Chem. Rev. 2002,
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M. Ittner, T. A. Reekie, J. Du, Q. Gao, D. E. Hibbs, M. Kassiou,
J. Med. Chem. 2019, 62, 8235; b) W. Maneerat, T. Ritthiwigrom,
S. Cheenpracha, T. Promgool, K. Yossathera, S. Deachathai, W.
Phakhodee, S. Laphookhieo, J. Nat. Prod. 2012, 75, 741; c) T.
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Matsuno, A. Asai, N. Asada, K. Kitaura, N. Fujii, J. Med. Chem.
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Acknowledgements
X. Tian and L. Song are grateful to the CSC (China Scholarship Council)
for a PhD fellowship.
[10]
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[12]
J. Luo, J. Zhang, ACS Catal. 2016, 6, 87.
J. Lia, A. C. Grimsdale, Chem. Soc. Rev. 2010, 39, 2399.
B. Witulski, C. Alayrac, Angew. Chem. Int. Ed. 2002, 41, 3281;
Angew. Chem. 2002, 114, 3415.
Keywords: sulfilimines • nitrenes • C–H insertions • C–H aminations
[13]
a) T. Wang, T. R. Hoye, J. Am. Chem. Soc. 2016, 138, 13870; b)
B. Baire, D. Niu, P. H. Willoughby, B. P. Woods, T. R. Hoye, Nat.
Protoc. 2013, 8, 501; c) M. F. Martínez-Esperón, D. Rodríguez,
L. Castedo, C. Saá, Org. Lett. 2005, 7, 2213.
• carbazoles
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L. Ackermann, A. Althammer, Angew. Chem. Int. Ed. 2007, 46,
1627; Angew. Chem. 2007, 119, 1652.
a) S. H. Cho, J. Yoon, S. Chang, J. Am. Chem. Soc. 2011, 133,
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a) T. V. Nykaza, A. Ramirez, T. S. Harrison, M. R. Luzung, A. T.
Radosevich, J. Am. Chem. Soc. 2018, 140, 3103; b) I. T. Alt, C.
Guttroff, B. Plietker, Angew. Chem. Int. Ed. 2017, 56, 10582;
Angew. Chem. 2017, 129, 10718; c) I. T. Alt, B, Plietker, Angew.
Chem. Int. Ed. 2016, 55, 1519; Angew. Chem. 2016, 128, 1542; d)
A. L. Pumphrey, H. Dong, T. G. Driver, Angew. Chem. Int. Ed.
2012, 51, 5920; Angew. Chem. 2012, 124, 6022; e) B. J. Stokes,
B. Jovanović, H. Dong, K. J. Richert, R. D. Riell, T. G. Driver, J.
Org. Chem. 2009, 74, 3225; f) M. Shen, B. E. Leslie, T. G. Driver,
Angew. Chem. Int. Ed. 2008, 47, 5056; Angew. Chem. 2008, 120,
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Selected reviews on nitrene chemistry: a) G. Dequirez, V. Pons,
P. Dauban, Angew. Chem. Int. Ed. 2012, 51, 7384; Angew. Chem.
2012, 124, 7498; b) P. Müller, C. Fruit, Chem. Rev. 2003, 103,
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For selected examples on nitrene transfer to alkynes, see: a) X.
Tian, L. Song, K. Farshadfar, M. Rudolph, F. Rominger, T. Oeser,
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129, 1046; e) H. Jin, L. Huang, J. Xie, M. Rudolph, F. Rominger,
A. S. K. Hashmi, Angew. Chem. Int. Ed. 2016, 55, 794; Angew.
Chem. 2016, 128, 804; f) A.-H. Zhou, Q. He, C. Shu, Y.-F. Yu, S.
Liu, T. Zhao, W. Zhang, X. Lu, L.-W. Ye, Chem. Sci. 2015, 6,
[16]
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