Synlett
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

Somadrita Borthakur
a   Applied Organic Chemistry, Chemical Sciences and Technology Division, CSIR-North East Institute of Science and Technology, Jorhat-785006, Assam, India
d   Department of Chemistry, Gauhati University, Gauhati-781014, Assam, India
,
Supriya Khundrakpam
a   Applied Organic Chemistry, Chemical Sciences and Technology Division, CSIR-North East Institute of Science and Technology, Jorhat-785006, Assam, India
b   Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, Uttar Pradesh, India
,
Sumi Changmai
a   Applied Organic Chemistry, Chemical Sciences and Technology Division, CSIR-North East Institute of Science and Technology, Jorhat-785006, Assam, India
b   Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, Uttar Pradesh, India
,
Bipul Sarma
c   Department of Chemical Sciences, Tezpur University, Tezpur-784028, Assam, India
,
Dilip Kakati
d   Department of Chemistry, Gauhati University, Gauhati-781014, Assam, India
,
Sanjib Gogoi
a   Applied Organic Chemistry, Chemical Sciences and Technology Division, CSIR-North East Institute of Science and Technology, Jorhat-785006, Assam, India
b   Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, Uttar Pradesh, India
› Author Affiliations

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.

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

  • 3 Maruo S, Nishio K, Sasamori T, Tokitoh N, Kuramochi K, Tsubaki K. Org. Lett. 2013; 15: 1556
  • 4 Zhou L, Wang C, Yuan C, Liu H, Zhang C, Guo H. Org. Lett. 2018; 20: 6591
    • 5a For a recent review, see: Duarah G, Kaishap PP, Begum T, Gogoi S. Adv. Synth. Catal. 2019; 361: 654

    • For a recent example, see:
    • 5b Borthakur S, Baruah S, Sarma B, Gogoi S. Org. Lett. 2019; 21: 2768
  • 7 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.
  • 8 Zeng R, Dong G. J. Am. Chem. Soc. 2015; 137: 1408
  • 9 CCDC 2422643 contains the supplementary crystallographic data for compound 3aa. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.