Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
Synthesis 2023; 55(21): 3568-3574
DOI: 10.1055/a-2092-9012
DOI: 10.1055/a-2092-9012
special topic
C–H Bond Functionalization of Heterocycles
Palladium-Catalyzed Dearomatization of Benzothiophenes: Isolation and Functionalization of a Discrete Dearomatized Intermediate
Generous financial support from the National Institute of General Medical Sciences of the National Institutes of Health (R35 GM124661) is gratefully acknowledged. This material is based upon work supported by the National Science Foundation through the Major Research Instrumentation Program under Grant No. CHE 1625543 and CHE-0923449, which was used to purchase the X-ray diffractometers and software used in this manuscript. This work was supported in part by the Research Instrumentation Center in the Department of Chemistry at Purdue University. Funding for the NMR instrumentation at the University of Kansas was provided by NIH Shared Instrumentation Grant # S10OD016360, NSF Major Research Instrumentation Grant # 9977422 and NIH Center Grant # P20GM103418.
Abstract
A Pd-catalyzed decarboxylative dearomatization reaction of a heterocyclic substrate enables access to an uncommon reaction intermediate that rearomatizes in the presence of amine bases in a net C–H functionalization sequence. The dearomatized benzo[b]thiophene intermediate bears an exocyclic alkene that can be functionalized through cycloaddition and halogenation reactions to deliver complex heterocyclic products.
Key words
transition metal - C–H functionalization - dearomatization - heterocycles - decarboxylationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2092-9012.
- Supporting Information
- CIF File
Publication History
Received: 01 February 2023
Accepted after revision: 12 May 2023
Accepted Manuscript online:
12 May 2023
Article published online:
13 June 2023
© 2023. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References
- 1 Davies HM. L, Morton D. J. Org. Chem. 2016; 81: 343
- 2 Guillemard L, Kaplaneris N, Ackermann L, Johansson MJ. Nat. Rev. Chem. 2021; 5: 522
- 3 Labinger JA, Bercaw JE. Nature 2002; 417: 507
- 4 Hartwig JF. J. Am. Chem. Soc. 2016; 138: 2
- 5 Gensch T, Hopkinson MN, Glorius F, Wencel-Delord J. Chem. Soc. Rev. 2016; 45: 2900
- 6 Yamaguchi J, Yamaguchi AD, Itami K. Angew. Chem. Int. Ed. 2012; 51: 8960
- 7 Tunge JA. Isr. J. Chem. 2020; 60: 351
- 8 He J, Wasa M, Chan KS. L, Shao Q, Yu JQ. Chem. Rev. 2017; 117: 8754
- 9 Zhang S, Yamamoto Y, Bao M. Adv. Synth. Catal. 2021; 363: 587
- 10 Li F, Zhang X, Renata H. Curr. Opin. Chem. Biol. 2019; 49: 25
- 11 Yang MH, Hunt JR, Sharifi N, Altman RA. Angew. Chem. Int. Ed. 2016; 55: 9080
- 12 Bao M, Nakamura H, Yamamoto Y. J. Am. Chem. Soc. 2001; 123: 759
- 13 Lu S, Xu Z, Bao M, Yamamoto Y. Angew. Chem. Int. Ed. 2008; 47: 4366
- 14 Li TR, Maliszewski ML, Xiao WJ, Tunge JA. Org. Lett. 2018; 20: 1730
- 15 Kayashima Y, Komatsuda M, Muto K, Yamaguchi J. Chem. Lett. 2020; 49: 836
- 16 Mendis SN, Tunge JA. Chem. Commun. 2016; 52: 7695
- 17 Recio A, Heinzman JD, Tunge JA. Chem. Commun. 2012; 48: 142
- 18 de Azambuja F, Yang M.-H, Feoktistova T, Selvaraju M, Brueckner AC, Grove MA, Koley S, Cheong PH.-Y, Altman RA. Nat. Chem. 2020; 12: 489
- 19 Tshepelevitsh S, Kütt A, Lõkov M, Kaljurand I, Saame J, Heering A, Plieger PG, Vianello R, Leito I. Eur. J. Org. Chem. 2019; 6735
- 20 CCDC 2237820 (1a), 2237821 (1b), and 2237648 (8) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
- 21 Becker MR, Wearing ER, Schindler CS. Nat. Chem. 2020; 12: 898
- 22 Soenen DR, Zimpleman JM, Boger DL. J. Org. Chem. 2003; 68: 3593