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Synlett
DOI: 10.1055/a-2599-1277
DOI: 10.1055/a-2599-1277
letter
Emerging Trends in Organic Chemistry: A Focus on India
Palladium(II)-Catalyzed Alkyne Annulation Reactions for the Synthesis of Cyclopenta[b]naphthalene-1,4-diones
The authors thank SERB and CSIR, New Delhi, for financially supporting us through the GPP-0367 (CRG/2019/00l898), HCP 049, HCP 050, and OLP 2084 projects.

Abstract
A palladium-catalyzed C–H activation and alkyne annulation reaction of 2-hydroxy-3-(2-thienyl)naphthalene-1,4-diones has been developed for the construction of biologically important cyclopenta[b]naphthalene-1,4-dione derivatives. This reaction proceeds through hydroxy-group-directed heteroaryl C(sp2)–H activation, insertion of two molecules of an alkyne, and dehydrative cyclization pathways.
Key words
annulation - C–H bond activation - cyclopentanaphthalenediones - palladium catalysis - alkyne insertionSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2599-1277.
- Supporting Information
Publication History
Received: 27 February 2025
Accepted after revision: 02 May 2025
Accepted Manuscript online:
02 May 2025
Article published online:
13 June 2025
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References and Notes
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4-[(1Z)-3-Oxo-1,2,3-triphenylprop-1-en-1-yl]-4-phenyl-4H-benzo[5,6]indeno[1,2-b]thiophene-5,10-dione (3aa); Typical Procedure
A mixture of 2-hydroxy-3-(2-thienyl)naphthalene-1,4-dione (1; 64 mg, 0.25 mmol) and alkyne 2a (89 mg, 0.5 mmol) was stirred with catalyst Pd(OAc)2 (4.0 mg, 10 mol%) and oxidant Cu(OAc)2·H2O (40 mg, 1.0 equiv) in the presence of Cs2CO3 (65 mg, 0.25 mmol) in t-AmOH (4.0 mL) under open air at 100 °C for 8 h. The crude product obtained after
the removal of the solvent in vacuo was purified by column chromatography [silica
gel (100–200 mesh), hexane–EtOAc (1:4)] to give a yellow solid; yield: 111 mg (73%);
mp 176–180 °C.
1H NMR (500 MHz, CDCl3): δ = 8.26 (d, J = 4.8 Hz, 1 H), 8.10 (d, J = 7.3 Hz, 1 H), 7.93–7.88 (m, 2 H), 7.73–7.66 (m, 4 H), 7.60 (t, J = 7.5, 1.3 Hz, 1 H), 7.32 (t, J = 7.2 Hz, 2 H), 7.19 (t, J = 7.6 Hz, 3 H), 7.12 (d, J = 7.2 Hz, 2 H), 6.97 (t, J = 7.7 Hz, 2 H), 6.95–6.87 (m, 2 H), 6.85–6.76 (m, 4 H), 6.71 (s, 2 H). 13C NMR (125 MHz CDCl3): δ = 194.8, 181.8, 180.7, 152.7, 143.0, 137.5, 137.3, 135.9, 135.8, 135.0, 134.1,
133.9, 132.7, 132.4, 132.3, 131.3, 130.8, 129.6, 129.3, 128.7, 127.7, 127.6, 127.3,
126.8, 126.7, 126.7, 126.5, 125.9, 125.7, 67.9. HRMS (ESI): m/z [M + H]+ calcd for C42H27O3S: 611.1680; found: 611.1683.
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Centre via www.ccdc.cam.ac.uk/structures.
For a recent example, see: