Chemo-, Stereo- and Regioselective Fluoroallylation/Annulation of Hydrazones with gem-Difluorocyclopropanes via Tunable Palladium/NHC Catalysis.

Publisher: Wiley-VCH Country of Publication: Germany NLM ID: 0370543 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1521-3773 (Electronic) Linking ISSN: 14337851 NLM ISO Abbreviation: Angew Chem Int Ed Engl Subsets: PubMed not MEDLINE; MEDLINE

Publication: <2004-> : Weinheim : Wiley-VCH
Original Publication: Weinheim/Bergstr. : New York, : Verlag Chemie ; Academic Press, c1962-

Defluorinative manipulation of polyfluorinated molecules has shown great promise due to its granting of synthetic versatility to inert C-F bonds. The development of chemo-, stereo- and regioselective strategies to realize highly efficient formation of either the linear/branched or E/Z products from gem-difluorocyclopropanes (gem-F 2 CPs) is a challenging task. Herein, we have realized palladium/NHC-catalyzed fluoroallylation/annulation of hydrazones with gem-F 2 CPs that incorporate the hydrazone N 2 moiety into the products. The thermodynamically unstable fluorinated E-allylation products with aryl ketone hydrazones were obtained for the first time, while the di-alkyl ketone hydrazones yielded the monofluorinated products with branched selectivity under similar reaction conditions. With aldehyde hydrazones, two kinds of pyrazoles were obtained via a defluorinative allylation/annulation cascade, in which different carbon atoms of gem-F 2 CPs could be incorporated into the pyrazole rings regiospecifically. DFT calculations revealed that the divergent selectivity was kinetically controlled and the final C-C bond formation proceeded through a 7-membered TS.
(© 2023 Wiley-VCH GmbH.)

.
D. O'Hagan, Chem. Soc. Rev. 2008, 37, 308-319;.
S. Purser, P. R. Moore, S. Swallow, V. Gouverneur, Chem. Soc. Rev. 2008, 37, 320-330;.
C. Ni, J. Hu, Chem. Soc. Rev. 2016, 45, 5441-5454;.
M. G. Campbell, T. Ritter, Chem. Rev. 2015, 115, 612-633.
 .
E. P. Gillis, K. J. Eastman, M. D. Hill, D. J. Donnelly, N. A. Meanwell, J. Med. Chem. 2015, 58, 8315-8359;.
Y. Zhou, J. Wang, Z. Gu, S. Wang, W. Zhu, J. L. Acena, V. A. Soloshonok, K. Izawa, H. Liu, Chem. Rev. 2016, 116, 422-518;.
A. D. Asandei, Chem. Rev. 2016, 116, 2244-2274;.
J. Moschner, V. Stulberg, R. Fernandes, S. Huhmann, J. Leppkes, B. Koksch, Chem. Rev. 2019, 119, 10718-10801;.
Y. Zafrani, G. Parvari, D. Amir, L. Ghindes-Azaria, S. Elias, A. Pevzner, G. Fridkin, A. Berliner, E. Gershonov, Y. Eichen, S. Saphier, S. Katalan, J. Med. Chem. 2021, 64, 4516-4531.
 .
T. Furuya, A. S. Kamlet, T. Ritter, Nature 2011, 473, 470-477;.
P. A. Champagne, J. Desroches, J.-D. Hamel, M. Vandamme, J.-F. Paquin, Chem. Rev. 2015, 115, 9073-9174;.
J.-W. Lee, M. T. Oliveira, H. B. Jang, S. Lee, D. Y. Chi, D. W. Kim, C. E. Song, Chem. Soc. Rev. 2016, 45, 4638-4650;.
Y. Zhu, J. Han, J. Wang, N. Shibata, M. Sodeoka, V. A. Soloshonok, J. A. S. Coelho, F. D. Toste, Chem. Rev. 2018, 118, 3887-3964;.
A. D. Dilman, V. V. Levin, Acc. Chem. Res. 2018, 51, 1272-1280;.
P. Xiao, X. Pannecoucke, J.-P. Bouillon, S. Couve-Bonnaire, Chem. Soc. Rev. 2021, 50, 6094-6151.
 .
H. Amii, K. Uneyama, Chem. Rev. 2009, 109, 2119-2183;.
T. Ahrens, J. Kohlmann, M. Ahrens, T. Braun, Chem. Rev. 2015, 115, 931-972;.
T. Fujita, K. Fuchibe, J. Ichikawa, Angew. Chem. Int. Ed. 2019, 58, 390-402;.
X. Ma, Q. Song, Chem. Soc. Rev. 2020, 49, 9197-9219;.
D. Ge, X.-Q. Chu, Org. Chem. Front. 2022, 9, 2013-2055.
 .
P. Tian, C. Feng, T. P. Loh, Nat. Commun. 2015, 6, 7472;.
W. H. Guo, Q. Q. Min, J. W. Gu, X. Zhang, Angew. Chem. Int. Ed. 2015, 54, 9075-9078;.
K. Fuchibe, H. Hatta, K. Oh, R. Oki, J. Ichikawa, Angew. Chem. Int. Ed. 2017, 56, 5890-5893;.
F. P. Wu, Y. Yuan, J. Liu, X. F. Wu, Angew. Chem. Int. Ed. 2021, 60, 8818-8822;.
Y.-J. Yu, F.-L. Zhang, T.-Y. Peng, C.-L. Wang, J. Cheng, C. Chen, K. N. Houk, Y.-F. Wang, Science 2021, 371, 1232-1240;.
T. T. Simur, T. Ye, Y.-J. Yu, F.-L. Zhang, Y.-F. Wang, Chin. Chem. Lett. 2022, 33, 1193-1198.
 .
W. R. Dolbier, M. A. Battiste, Chem. Rev. 2003, 103, 1071-1098;.
M. Fedoryński, Chem. Rev. 2003, 103, 1099-1132;.
Y. Zhu, Y. Zeng, Z.-T. Jiang, Y. Xia, Synlett 2023, 34, 29-39;.
L. Lv, H. Qian, Z. Li, ChemCatChem 2022, 14, e202200890.
 .
P. Van der Veken, K. Senten, I. Kertèsz, I. De Meester, A.-M. Lambeir, M.-B. Maes, S. Scharpé, A. Haemers, K. Augustyns, J. Med. Chem. 2005, 48, 1768-1780;.
N. A. Meanwell, J. Med. Chem. 2018, 61, 5822-5880.
J. Xu, E. A. Ahmed, B. Xiao, Q. Q. Lu, Y. L. Wang, C. G. Yu, Y. Fu, Angew. Chem. Int. Ed. 2015, 54, 8231-8235.
 .
E. M. A. Ahmed, A. M. Y. Suliman, T.-J. Gong, Y. Fu, Org. Lett. 2019, 21, 5645-5649;.
E. M. A. Ahmed, A. M. Y. Suliman, T.-J. Gong, Y. Fu, Org. Lett. 2020, 22, 1414-1419;.
A. M. Y. Suliman, E. M. A. Ahmed, T.-J. Gong, Y. Fu, Org. Lett. 2021, 23, 3259-3263;.
A. M. Y. Suliman, E. M. A. Ahmed, T.-J. Gong, Y. Fu, Chem. Commun. 2021, 57, 6400-6403.
 .
J. Ni, B. Nishonov, A. Pardaev, A. Zhang, J. Org. Chem. 2019, 84, 13646-13654;.
Z. Fu, J. Zhu, S. Guo, A. Lin, Chem. Commun. 2021, 57, 1262-1265;.
P. X. Zhou, X. Yang, J. Wang, C. Ge, W. Feng, Y. M. Liang, Y. Zhang, Org. Lett. 2021, 23, 4920-4924;.
L. Wu, M. Wang, Y. Liang, Z. Shi, Chin. J. Chem. 2022, 40, 2345-2355;.
L. Lv, H. Qian, Y. Ma, S. Huang, X. Yan, Z. Li, Chem. Sci. 2021, 12, 15511-15518;.
L. Lv, H. Qian, A. B. Crowell, S. Chen, Z. Li, ACS Catal. 2022, 12, 6495-6505;.
Z. T. Jiang, J. Huang, Y. Zeng, F. Hu, Y. Xia, Angew. Chem. Int. Ed. 2021, 60, 10626-10631;.
Y. Zeng, H. Gao, Y. Zhu, Z.-T. Jiang, G. Lu, Y. Xia, ACS Catal. 2022, 12, 8857-8867;.
Y. Zeng, H. Yang, J. Du, Q. Huang, G. Huang, Y. Xia, Chem. Sci. 2022, 13, 12419-12425.
B. Xiong, X. Chen, J. Liu, X. Zhang, Y. Xia, Z. Lian, ACS Catal. 2021, 11, 11960-11965.
 .
Y. Xia, D. Qiu, J. Wang, Chem. Rev. 2017, 117, 13810-13889;.
Y. Xia, J. Wang, J. Am. Chem. Soc. 2020, 142, 10592-10605;.
D. K. Kölmel, E. T. Kool, Chem. Rev. 2017, 117, 10358-10376;.
P. Xu, W. Li, J. Xie, C. Zhu, Acc. Chem. Res. 2018, 51, 484-495;.
Z. Liu, P. Sivaguru, G. Zanoni, X. Bi, Acc. Chem. Res. 2022, 55, 1763-1781.
 .
K. E. Lutz, R. J. Thomson, Angew. Chem. Int. Ed. 2011, 50, 4437-4440;.
A. Prieto, R. Melot, D. Bouyssi, N. Monteiro, Angew. Chem. Int. Ed. 2016, 55, 1885-1889;.
S. Kobayashi, Y. Mori, J. S. Fossey, M. M. Salter, Chem. Rev. 2011, 111, 2626-2704;.
R. Lazny, A. Nodzewska, Chem. Rev. 2010, 110, 1386-1434.
 .
B. Lu, B. Feng, H. Ye, J.-R. Chen, W.-J. Xiao, Org. Lett. 2018, 20, 3473-3476;.
S. Breitler, E. M. Carreira, J. Am. Chem. Soc. 2015, 137, 5296-5299;.
S. Huang, G. P. Zhang, Y. J. Jiang, F. L. Yu, C. H. Ding, X. L. Hou, Chem. Commun. 2022, 58, 3513-3516;.
S. Huang, F. F. Tong, D. C. Bai, G. P. Zhang, Y. J. Jiang, B. Zhang, X. Leng, Y. L. Guo, X. L. Wan, X. Zhang, C. H. Ding, X. L. Hou, Nat. Commun. 2021, 12, 6551-6560;.
X.-J. Dai, C.-C. Li, C.-J. Li, Chem. Soc. Rev. 2021, 50, 10733-10742.
L. Lv, C.-J. Li, Angew. Chem. Int. Ed. 2021, 60, 13098-13104.
 .
S. Fustero, M. Sánchez-Roselló, P. Barrio, A. Simón-Fuentes, Chem. Rev. 2011, 111, 6984-7034;.
P. K. Mykhailiuk, Chem. Rev. 2021, 121, 1670-1715.
 .
J. A. Keith, D. C. Behenna, N. Sherden, J. T. Mohr, S. Ma, S. C. Marinescu, R. J. Nielsen, J. Oxgaard, B. M. Stoltz, W. A. Goddard, J. Am. Chem. Soc. 2012, 134, 19050-19060;.
M. J. Ardolino, J. P. Morken, J. Am. Chem. Soc. 2014, 136, 7092-7100;.
D.-C. Bai, F.-L. Yu, W.-Y. Wang, D. Chen, H. Li, Q.-R. Liu, C.-H. Ding, B. Chen, X.-L. Hou, Nat. Commun. 2016, 7, 11806;.
L. Lv, H. Qian, Green Synth. Catal. 2023, https://doi.org/10.1016/j.gresc.2023.01.006.
D. Zhu, L. Lv, C. C. Li, S. Ung, J. Gao, C.-J. Li, Angew. Chem. Int. Ed. 2018, 57, 16520-16524.

22201300 National Natural Science Foundation of China; 22071266 National Natural Science Foundation of China; 21XNLG04 the Fundamental Research Funds for the Central Universities, and the Research Funds of Renmin University of China; NSF MRI 1427949 the SCIURus, the Oberlin College HPC cluster; XSEDE TG-CHE210088 the research allocations awarded by Extreme Science and Engineering Discovery Environment

Keywords: C−F Bond Cleavage; Gem-Difluorocyclopropane; Hydrazone; Pyrazole; Regioselectivity

Date Created: 20230404 Date Completed: 20230525 Latest Revision: 20230525

20230525

10.1002/anie.202303271

37013706