RSS-Feed abonnieren
Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.
https://www.thieme-connect.de/rss/thieme/de/10.1055-s-00000083.xml
PDF herunterladen
Synlett 2022; 33(20): 2009-2012
DOI: 10.1055/a-1938-0643
DOI: 10.1055/a-1938-0643
letter
Transition-Metal-Free Synthesis of 3-Ethynylcoumarins by a DBU-Promoted Intramolecular Morita–Baylis–Hillman-Type Reaction/Dehydration/Isomerization Cascade
Authors
We thank the Natural Science Foundation of Zhejiang Province (Grant LTZ22B020002 and Grant LY20B020012) and Fundamental Research Funds for the Central Universities (2022CDJXY-025) for their financial support of this work.
Abstract
A transition-metal-free synthesis of 3-ethynylcoumarins from salicylaldehyde-derived alkynoates was developed involving a DBU-promoted intramolecular Morita–Baylis–Hillman-type reaction/dehydration/isomerization cascade. A wide variety of alkynoates were employed to deliver 3-ethynylcoumarins in moderate to good yields.
Key words
transition-metal-free reaction - ethynylcoumarins - Morita–Baylis–Hillman reaction - step economy - cascade reactionSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1938-0643.
- Supporting Information (PDF)
Publikationsverlauf
Eingereicht: 02. August 2022
Angenommen nach Revision: 07. September 2022
Accepted Manuscript online:
07. September 2022
Artikel online veröffentlicht:
17. Oktober 2022
© 2022. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References and Notes
- 1a Elangovan A, Lin J.-H, Yang S.-W, Hsu H.-Y, Ho T.-I. J. Org. Chem. 2004; 69: 8086 , Corigendum: J. Org. Chem., 2005; 70:1104
- 1b Sun H, Guo H, Wu W, Liu X, Zhao J. Dalton Trans. 2011; 40: 7834
- 1c Hammer CA, Falahati K, Jakob A, Klimek R, Burghardt I, Heckel A, Wachtveitl J. J. Phys. Chem. Lett. 2018; 9: 1448
- 1d Li C, Wang D, Xue W, Peng J, Wang T, Zhang Z. Dyes Pigm. 2021; 186: 108956
- 2a Yee DJ, Balsanek V, Sames D. J. Am. Chem. Soc. 2004; 126: 2282
- 2b Lee D.-N, Kim G.-J, Kim H.-J. Tetrahedron Lett. 2009; 50: 4766
- 2c Myung N, Connelly S, Kim B, Park SJ, Wilson IA, Kelly JW, Choi S. Chem. Commun. 2013; 49: 9188
- 2d Hu Q, Tan Y, Liu M, Yu J, Cui Y, Yang Y. Dyes Pigm. 2014; 107: 45
- 2e Depauw A, Dossi E, Kumar N, Fiorini-Debuisschert C, Huberfeld G, Ha-Thi M.-H, Rouach N, Leray I. Chem. Eur. J. 2016; 22: 14902
- 2f Sansalone L, Tang S, Garcia-Amorós J, Zhang Y, Nonell S, Baker JD, Captain B, Raymo FM. ACS Sens. 2018; 3: 1347
- 3a Le Bras G, Radanyi C, Peyrat J.-F, Brion J.-D, Alami M, Marsaud V, Stella B, Renoir J.-M. J. Med. Chem. 2007; 50: 6189
- 3b Stefani HA, Gueogjan K, Manarin F, Farsky SH. P, Zukerman-Schpector J, Caracelli I, Pizano Rodriguese SR, Muscará MN, Teixeira SA, Santin JR, Machado ID, Bolonheis SM, Curi R, Vinolo MA. Eur. J. Med. Chem. 2012; 58: 117
- 3c Woll MG, Chen G, Choi S, Dakka A, Huang S, Karp GM, Lee C.-S, Li C, Narasimhan J, Naryshkin N, Paushkin S, Qi H, Turpoff AA, Weetall MI. Welch E, Yang T, Zhang N, Zhao X, Pinard E, Ratni H. WO 2013101974, 2013
- 3d Woll MG, Qi H, Turpoff A, Zhang N, Zhang X, Chen G, Li C, Huang S, Yang T, Moon Y.-C, Lee C.-S, Choi S, Almstead NG, Naryshkin NA, Dakka A, Narasimhan J, Gabbeta V, Welch E, Zhao X, Risher N, Sheedy J, Weetall M, Karp GM. J. Med. Chem. 2016; 59: 6070
- 4 Zhang K.-M, Dou W, Li P.-X, Shen R, Ru J.-X, Liu W, Cui Y.-M, Chen C.-Y, Liu W.-S, Bai D.-C. Biosens. Bioelectron. 2015; 64: 542
- 5a Ast S, Schwarze T, Müller H, Sukhanov A, Michaelis S, Wegener J, Wolfbeis OS, Körzdörfer T, Dürkop A, Holdt H.-J. Chem. Eur. J. 2013; 19: 14911
- 5b Schwarze T, Riemer J, Eidner S, Holdt H.-J. Chem. Eur. J. 2015; 21: 11306
- 6 Liu Y, Zhang S, Lv X, Sun Y.-Q, Liu J, Guo W. Analyst 2014; 139: 4081
- 7a Gao Y, Zeng F, Sun X, Zeng M, Yang Z, Huang X, Shen G, Tan Y, Feng R, Qi C. Adv. Synth. Catal. 2018; 360: 1328
- 7b Wu X, Jia M, Huang M, Kim JK, Zhao Z, Liu J, Xi J, Li Y, Wu Y. Org. Biomol. Chem. 2020; 18: 3346
- 8 Mansaray JK, Sun J, Huang S, Yao W. Synlett 2019; 30: 809
- 9 Deng Z.-X, Zheng Y, Xie Z.-Z, Gao Y.-H, Xiao J.-A, Xie S.-Q, Xiang H.-Y, Chen X.-Q, Yang H. Org. Lett. 2020; 22: 488
- 10 Vagh SS, Hou B.-J, Edukondalu A, Wang P.-C, Lin W. Org. Lett. 2021; 23: 842
- 11 3-Ethynylcoumarins 3a–p; General Procedure DBU (0.6 mmol, 90 μL) was added to a suspension of the appropriate 2-formylphenylbutynoate 2 (0.5 mmol) and 4 Å MS (100 mg) in anhydrous (CH2Cl)2 (10 mL) under N2 in a dry Schlenk tube at r.t., and the resulting mixture was stirred at r.t. until the substrate was fully consumed (TLC, ~0.5 h). The mixture was filtered and the filter was washed with CH2Cl2. The filtrate was concentrated, and the residue was purified by flash column chromatography (silica gel, PE–EtOAc). 3-Ethynyl-7-methyl-2H-chromen-2-one (3b) White solid; yield: 47.9 mg (52%); mp 182.0–186.3 °C. IR (KBr): 3235, 3045, 2926, 2101, 1721, 1616, 1604, 1423 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.90 (s, 1 H), 7.35 (d, J = 7.8 Hz, 1 H), 7.12 (s, 1 H), 7.11 (d, J = 8.5 Hz, 1 H), 3.34 (s, 1 H), 2.45 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 159.6, 153.6, 146.6, 144.3, 127.5, 126.1, 117.0, 116.1, 110.6, 83.2, 77.4, 21.9. HRMS (ESI): m/z [M+H]+ calcd for C12H9O2: 185.0597; found: 185.0604.
- 12 Mondal A, Hazra R, Grover J, Raghuand M, Ramasastry SS. V. ACS Catal. 2018; 8: 2748
For selected references, see: