10.1002/chem.201904994
Chemistry - A European Journal
COMMUNICATION
Ph
H
Ph
Ph
H
[4]
a) L. W. Ciszewski, K. Rybicka-Jasinska, D. Gryko, Org. Biomol. Chem.
2019, 17, 432-448; b) N. R. Candeias, C. A. M. Afonso, Curr. Org.
Chem. 2009, 13, 763; c) O. S. Galkina, L. L. Rodina, Russ. Chem. Rev.
2016, 85, 537; d) C. Empel, R. M. Koenigs, Synlett, 2019, 30, 1929-
1934.
H
O
O
O
O
F
O
O
O
N
N
N
O
O
O
O
[5]
[6]
Selected references: a) Z. Wang, A. G. Herraiz, A. M. del Hoyo, M. G.
Suero, Nature 2018, 554, 86-91; b) Y. S. Mimieux Vaske, M. E.
Mahoney, J. P. Konopelski, D. L. Rogow, W. J. McDonald, J. Am.
Chem. Soc. 2010, 132, 11379-11385.
16b, 70%
d.r. >20:1
15, 54%
d.r. 1.2:1
16a, 65%
d.r. >20:1
O
Ph
Ph
H
H
O
O
F
O
O
O
N
H
a) I. Jurberg, H. M. L. Davies, Chem. Sci. 2018, 9, 5112; b) R.
Hommelsheim, Y. Guo, Z. Yang, C. Empel, R. M. Koenigs, Angew.
Chem. Int. Ed. 2019, 58, 1203-1207; Angew. Chem. 2019, 131, 1216-
1220; c) F. He, R. M. Koenigs, Chem. Commun. 2019, 55, 4881-4884;
d) X. Zhang, C. Du, H. Zhang, X.-C. Li, Y.-L. Wang, J.-L. Niu, M.-P.
Song, Synthesis, 2019, 51, 889. (e) Z. Zhang, D. Yadagiri, V.
Gevorgyan, Chem. Sci. 2019, 10, 8399-8404. (f) Y. Guo, T. V. Nguyen,
R. M. Koenigs, Org. Lett. 2019,21, 8814-8818; (g) T. Chidley, I. Jameel,
S. Rizwan, P. A. Peixoto, L. Pouysegu, S. Quideau, W. S. Williams, G.
K. Murphy, Angew. Chem. Int. Ed. 2019, 58, 16959-16965; Angew.
Chem. 2019, 131, 17115-17121.
N
O
O
16d, 78 %
d.r. >20:1
16c, 68%
d.r. >20:1
Ph
Ph
H
H
H
O
O
O
O
S
S
H
17, 43%
18, 56%
[7]
a) S. Jana, R. M. Koenigs, Asian J. Org. Chem. 2019, 8, 683-686; b) Z.
Yang, Y. Guo, R. M. Koenigs, Chem. Eur. J. 2019, 25, 6703-6706; c) J.
Yang, J. Wang, H. Huang, G. Qin, Y. Jiang, T. Xiao, Org. Lett. 2019, 21,
2654; d) Z. Yang, Y. Guo, R. M. Koenigs, Chem. Commun. 2019, 55,
8410-8413; e) S. Jana, Z. Yang, C. Pei, X. Xu, R. M. Koenigs, Chem.
Sci. 2019,10, 10129-10134; f) F. He, C. Pei, R. M. Koenigs, Chem.
Commun. 2019, DOI: 10.1039/c9cc08888a.
Scheme 6. Cyclopropanation of heterocycles under stoichiometric conditions.
In summary, we could demonstrate that photochemical carbene
transfer reactions can now be conducted under stoichiometric
reaction conditions using a protocol that provides an in situ
access to aryldiazoacetates from tosyl hydrazones under
Bamford Stevens conditions at ambient temperature. The in situ
generation of diazoesters is pivotal to reduce the concentration
of the diazoester in the reaction solution and to thus reduce
unwanted side reactions. This strategy now allows efficient
metal-free C-H, N-H functionalization and cyclopropanation
reactions of heterocycles under mild and operationally simple
reaction conditions and avoids the use of toxic diazoalkane
reaction partners.
[8]
[9]
T. Xiao, M. Mei, Y. He, L. Zhou, Chem. Commun. 2018, 54, 8865.
C. Empel, F. W. Patureau, R. M. Koenigs, J. Org. Chem. 2019, 84,
11316-11322.
[10] Selected references: a) J. R. Fulton, V. K. Aggarwal, J. de Vicente, Eur.
J. Org. Chem. 2005, 1479-1492; b) Y. Xia, J. Wang, Chem. Soc. Rev.
2017, 46, 2306-2362; c) M. Jia, S. Ma, Angew. Chem. Int. Ed. 2016, 55,
9134-9166; Angew. Chem. 2016, 128, 9280-9313; d) C.-L. Sun, Z.-J.
Shi, Chem. Rev. 2014, 114, 9219-9280; e) Z. Shao, H. Zhang, Chem.
Soc. Rev. 2012, 41, 560-572; f) J. Barluenga, C. Valdes, Angew. Chem.
Int. Ed. 2011, 50, 7486-7500; Angew. Chem. 2011, 123, 7626-7640.
[11] Selected references: a) P. K. Mykhailiuk, R. M. Koenigs, Chem. Eur. J.
2019, DOI: 10.1002/chem201903335; b) B. Morandi, E. M. Carreira,
Angew. Chem. Int. Ed. 2010, 49, 938-941; Angew. Chem. 2010, 122,
950-953; c) K. J. Hock, R. Spitzner, R. M. Koenigs, Green Chem. 2017,
19, 905-909; d) K. J. Hock, L. Mertens, R. Hommelsheim, R. Spitzner,
R. M. Koenigs, Chem. Commun. 2017, 53, 6577-6580; e) P. K.
Mykhailiuk, Eur. J. Org. Chem. 2015, 7235-7239; f) P. K. Mykhailiuk,
Org. Biomol. Chem. 2017, 15, 7296-7301; g) P. K. Mykhailiuk, Angew.
Chem. Int. Ed. 2015, 54, 6558-6561; Angew. Chem. 2015, 127, 6658-
6661.
Acknowledgements
The authors thank the Deutsche Forschungsgemeinschaft (DFG,
German Research Foundation) – project no. 408033718.
Keywords: photochemistry • carbene • C-H functionalization •
N-H functionalization • cyclopropanation
[12] For details, see supporting information.
[13] Selected articles: a) M. Delgado-Rebollo, A. Prieto, P. J. Pérez,
ChemCatChem 2014, 6, 2047-2052; b) M. Sarkar, P. Daw, T. Ghatak, J.
K. Bera, Chem. Eur. J. 2014, 20, 16537-16549; c) G. Özüduru, T.
Schubach, M. M. Boyson, Org. Lett., 2012, 14, 4990-4993; d) F. Gnad,
M. Poleschak, O. Reiser, Tetrahedron Lett. 2004, 45, 4277-4280; e) Y.
Cai, S.-F. Zhu, G.-P. Wang, Q.-L. Zhou, Adv. Synth. Catal. 2011, 353,
2939-2944.
[1]
[2]
H. Meerwein, H. Rathjen, H. Werner, Ber. Dtsch. Chem. Ges. A/B,
1942, 75, 1610-1622.
Selected review articles on the functionalization of C-H bonds: a) S. A.
Girard, T. Knauber, C.-J. Li, Angew. Chem. Int. Ed. 2014, 53, 74-100;
Angew. Chem. 2014, 126, 76-103; b) B. Li, P. H. Dixneuf, Chem. Soc.
Rev. 2013, 42, 5744-5767; c) T. Gensch, M. N. Hopkinson, F. Glorius, J.
Wencel-Delord, Chem. Soc. Rev. 2016, 45, 2900-2936; d) M. Moselage,
J. Lie, L. Ackermann, ACS Catal. 2016, 6, 498-525; S.-F. Zhu, Q.-L.
Zhou, Natl. Sci. Rev. 2014, 1, 580-603; g) R. Shang, L. Ilies, E.
Nakamura, Chem. Rev. 2017, 117, 9086-9139.
[14] M. Sarkar, P. Daw, T. Ghatak, J. K. Bera, Chem. Eur. J. 2014, 20,
16537-16549.
[15] K. J. Hock, A. Knorrscheidt, R. Hommelsheim, J. Ho, M. J.
Weissenborn, R. M. Koenigs, Angew. Chem., Int. Ed. 2019, 58, 3630-
3634; Angew. Chem. 2019, 131, 3669-3673.
[3]
Selected articles on precious metal-catalyzed C-H functionalization
reactions: a) H. M. L. Davies, J. R. Manning, Nature 2018, 451, 417-
424; b) A. Ford, H. Miel, A. Ring, C. N. Slattery, A. R. Maguire, M. A.
McKervey, Chem. Rev. 2015, 115, 9981-10080; c) M. P. Doyle, R.
Duffy, M. Ratnikov, Z. Zhou, Chem. Rev. 2010, 110, 704-724; d) Y. Xia,
D. Qiu, J. Wang, Chem. Rev. 2017, 117, 13810-13889.
[16] V. Arredondo, S. C. Hiew, E. S. Gutman, I. D. U. A. Premachandra, D.
van Vranken, Angew. Chem. Int. Ed. 2017, 56, 4156-4159; Angew.
Chem. 2017, 129, 4220-4223.
[17] G. Xu, K. Liu, J. Sun, Org. Lett. 2018, 20, 72-75.
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