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Palladium(0)-catalyzed aryne annulation: a powerful strategy for the synthesis of thio-bridged compounds

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Abstract

A method for the construction of various thio-bridged compounds is developed using readily available o-(trimethylsilyl)aryl triflates as a source of aryne precursor, catalyzed by simple Pd(dba)2/dppe complex. This operationally simple and modular protocol allows thio-bridged compound via C(sp2)-C(sp2) and C(sp2)-C(sp3) bond formation in promising yields with a broad substrate scope. The key part is in situ generation of an aryne from o-(trimethylsilyl)aryl triflates and their subsequent intermolecular annulation.

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References

  1. Khan FA, Dash J (2002) Synthesis of a novel, highly symmetric bis-oxa-bridged compound. J Am Chem Soc 124(11):2424–2425. https://doi.org/10.1021/ja017371f

    Article  CAS  Google Scholar 

  2. Khan FA, Dash J, Sudheer C, Sahu N, Parasuraman K (2005) Concise synthesis of novel oxa-bridged compounds. J Org Chem 70(19):7565–7577. https://doi.org/10.1021/jo0507385

    Article  CAS  Google Scholar 

  3. Zhao W (2010) Novel syntheses of bridge-containing organic compounds. Chem Rev 110(3):1706–1745. https://doi.org/10.1021/cr9002402

    Article  CAS  Google Scholar 

  4. Wu T, Tang W (2021) Construction of bridged polycyclic skeletons via transition-metal catalyzed carbon-carbon bond-forming reactions. Chem Eur J 27(12):3944–3956. https://doi.org/10.1002/chem.202003863

    Article  CAS  Google Scholar 

  5. Paterson I, Razzak M, Anderson EA (2008) Total synthesis of (−)-saliniketals A and B. Org Lett 10(15):3295–3298. https://doi.org/10.1021/ol801148d

    Article  CAS  Google Scholar 

  6. Ueno A, Kitawaki T, Chida N (2008) Total synthesis of (±)-Murrayazoline. Org Lett 10(10):1999–2002. https://doi.org/10.1021/ol800602v

    Article  CAS  Google Scholar 

  7. Shenvi RA, Guerrero CA, Shi J, Li CC, Baran PS (2008) Synthesis of (+)-cortistatin A. J Am Chem Soc 130(23):7241–7243. https://doi.org/10.1021/ja8023466

    Article  CAS  Google Scholar 

  8. Chen J, Chen X, Bois-Choussy M, Zhu J (2006) Total synthesis of ecteinascidin 743. J Am Chem Soc 128(1):87–89. https://doi.org/10.1021/ja0571794

    Article  CAS  Google Scholar 

  9. Greshock TJ, Funk RL (2006) An approach to the total synthesis of welwistatin. Org Lett 8(12):2643–2645. https://doi.org/10.1021/ol0608799

    Article  CAS  Google Scholar 

  10. Nicolaou KE, Lim YH, Becker J (2009) Total synthesis and absolute configuration of the bisanthraquinone antibiotic BE-43472B. Angew Chem Int Ed 48(19):3444–3448. https://doi.org/10.1002/anie.200900058

    Article  CAS  Google Scholar 

  11. Bhunia A, Yetra SR, Biju AT (2012) Recent advances in transition-metal-free carbon–carbon and carbon–heteroatom bond-forming reactions using arynes. Chem Soc Rev 41(8):3140–3152. https://doi.org/10.1039/C2CS15310F

    Article  CAS  Google Scholar 

  12. Dubrovskiy AV, Markina NA, Larock RC (2013) Use of benzynes for the synthesis of heterocycles. Org Biomol Chem 11(2):191–218. https://doi.org/10.1039/C2OB26673C

    Article  CAS  Google Scholar 

  13. Asamdi M, Chikhalia KH (2017) Aryne insertion into σ bonds. Asian J Org Chem 6(10):1331–1348. https://doi.org/10.1002/ajoc.201700284

    Article  CAS  Google Scholar 

  14. Dhokale RA, Mhaske SB (2018) Transition-metal-catalyzed reactions involving arynes. Synthesis 50(01):1–16. https://doi.org/10.1055/s-0036-1589517

    Article  CAS  Google Scholar 

  15. Takikawa H, Nishii A, Sakai T, Suzuki K (2018) Aryne-based strategy in the total synthesis of naturally occurring polycyclic compounds. Chem Soc Rev 47(21):8030–8056. https://doi.org/10.1039/C8CS00350E

    Article  CAS  Google Scholar 

  16. Himeshima Y, Sonoda T, Kobayashi H (1983) Fluoride-induced 1, 2-elimination of o-trimethylsilylphenyl triflate to benzyne under mild conditions. Chem Lett 12(8):1211–1214. https://doi.org/10.1246/cl.1983.1211

    Article  Google Scholar 

  17. Wu C, Fang Y, Larock RC, Shi F (2010) Synthesis of 2 H-indazoles by the [3+ 2] cycloaddition of arynes and sydnones. Org Lett 12(10):2234–2237. https://doi.org/10.1021/ol100586r

    Article  CAS  Google Scholar 

  18. Ren H, Luo Y, Ye S, Wu J (2011) Silver triflate catalyzed reaction of 2-alkynylbenzaldoxime with aryne. Org Lett 13(10):2552–2555. https://doi.org/10.1021/ol200629y

    Article  CAS  Google Scholar 

  19. Sha F, Huang X (2009) A multicomponent reaction of arynes, isocyanides, and terminal alkynes: highly chemo-and regioselective synthesis of polysubstituted pyridines and isoquinolines. Angew Chem Int Ed 121(19):3510–3513. https://doi.org/10.1002/ange.200900212

    Article  Google Scholar 

  20. Huang X, Zhang T (2010) Cascade nucleophilic addition—Cyclic michael addition of arynes and phenols/anilines bearing ortho α, β-unsaturated groups: facile synthesis of 9-functionalized xanthenes/acridines. J Org Chem 75(2):506–509. https://doi.org/10.1021/jo902311a

    Article  CAS  Google Scholar 

  21. Pintori DG, Greaney MF (2010) Insertion of benzene rings into the amide bond: one-step synthesis of acridines and acridones from aryl amides. Org Lett 12(1):168–171. https://doi.org/10.1021/ol902568x

    Article  CAS  Google Scholar 

  22. Samineni R, Bandi CRC, Srihari P, Mehta G (2016) Multiple aryne insertions into oxindoles: synthesis of bioactive 3, 3-diarylated oxindoles and dibenzo [b, e] azepin-6-ones. Org Lett 18(23):6184–6187. https://doi.org/10.1021/acs.orglett.6b03224

    Article  CAS  Google Scholar 

  23. Li RJ, Pi SF, Liang Y, Wang ZQ, Song RJ, Chen GX, Li JH (2010) Palladium-catalyzed annulations of arynes with 2-(2-iodophenoxy)-1-substituted ethanones. Chem commun 46(43):8183–8185. https://doi.org/10.1039/C0CC02720K

    Article  CAS  Google Scholar 

  24. Bhojgude SS, Bhunia A, Biju AT (2016) Employing arynes in diels-alder reactions and transition-metal-free multicomponent coupling and arylation reactions. Acc Chem Res 49(9):1658–1670. https://doi.org/10.1021/acs.accounts.6b00188

    Article  CAS  Google Scholar 

  25. Kalvacherla B, Batthula S, Balasubramanian S, Palakodety RK (2018) Transition-metal-free cyclization of propargylic alcohols with aryne: synthesis of 3-benzofuranyl-2-oxindole and 3-spirooxindole benzofuran derivatives⊥. Org Lett 20(13):3824–3828. https://doi.org/10.1021/acs.orglett.8b01414

    Article  CAS  Google Scholar 

  26. Saputra A, Fan R, Yao T, Chen J, Tan J (2020) Synthesis of 2-(Arylthio) indolenines via chemoselective arylation of thio-oxindoles with arynes. Adv. Syn. Catal. 362(13):2683–2688

    Article  CAS  Google Scholar 

  27. Yousaf M, Zahoor AF, Akhtar R, Ahmad M, Naheed S (2020) Development of green methodologies for Heck, Chan-Lam, Stille and Suzuki cross-coupling reactions. Mol Divers 24(3):821–839. https://doi.org/10.1007/s11030-019-09988-7

    Article  CAS  Google Scholar 

  28. Munir I, Zahoor AF, Rasool N, Naqvi SAR, Zia KM, Ahmad R (2019) Synthetic applications and methodology development of Chan-Lam coupling: a review. Mol Divers 23(1):215–259. https://doi.org/10.1007/s11030-018-9870-z

    Article  CAS  Google Scholar 

  29. Wang Q, Dai Z, Di X, Huang Q, Wang Y, Zhu J (2020) Pd (NHC)(cinnamyl) Cl-catalyzed Suzuki cross-coupling reaction of aryl sulfonates with arylboronic acids. Mol Divers 24(4):903–911. https://doi.org/10.1007/s11030-019-10001-4

    Article  CAS  Google Scholar 

  30. Heravi MM, Mohammadi P (2021) Layered double hydroxides as heterogeneous catalyst systems in the cross-coupling reactions: an overview. Mol Divers. https://doi.org/10.1007/s11030-020-10170-7

    Article  Google Scholar 

  31. Tabassum S, Zahoor AF, Ahmad S, Noreen R, Khan SG, Ahmad H (2021) Cross-coupling reactions towards the synthesis of natural products. Mol Divers. https://doi.org/10.1007/s11030-021-10195-6

    Article  Google Scholar 

  32. Morja MI, Patel JJ, Chauhan PM, Chikhalia KH (2020) An efficient synthesis of strained thio-bridged compounds via Pd (0) catalyzed intramolecular Csp2 (aryl)-Csp3 (alkyl) cross dehydrohalogenative coupling reaction. Tetrahedron 76(34):131348. https://doi.org/10.1016/j.tet.2020.131348

    Article  CAS  Google Scholar 

  33. Chauhan PM, Morja MI, Asamdi M, Chikhalia KH (2020) Copper catalyzed cyanomethylation reaction of 4-thiazolidinone. Tetrahedron Lett 61(50):152601. https://doi.org/10.1016/j.tetlet.2020.152601

    Article  CAS  Google Scholar 

  34. Morja MI, Chauhan PM, Chikhalia KH (2021) Palladium (II)-catalyzed direct annulation of 2-chloronicotinaldehyde with 2-bromothiophenol via novel C (formyl)-C (aryl) coupling strategy. Res Chem Intermed 47(11):4513–4524. https://doi.org/10.1007/s11164-021-04536-1

    Article  CAS  Google Scholar 

  35. Morja MI, Chauhan PM, Chikhalia KH (2021) Palladium-catalyzed novel C (formyl)-C (aryl)/C (aryl)-N (amine) coupling sequence between 2-(Methylamino) nicotinaldehyde and 3-Bromo-2-chlorothiophene: an efficient construction of 4-pyridone fused hybrid scaffolds. ChemistrySelect 6(20):5014–5020. https://doi.org/10.1002/slct.202100790

    Article  CAS  Google Scholar 

  36. Morja MI, Chauhan PM, Chikhalia KH (2021) Iron catalyzed alkynylation of thiohydantoins with terminal alkyne via cross-dehydrogenative coupling (CDC). Tetrahedron Lett 77:153148. https://doi.org/10.1016/j.tetlet.2021.153148

    Article  CAS  Google Scholar 

  37. Patel RB, Desai PS, Desai KR, Chikhalia KH (2006) Synthesis of pyrimidine based thiazolidinones and azetidinones: antimicrobial and antitubercular agents. Indian J Chem 45B:773–778

    CAS  Google Scholar 

  38. Liu Z, Zhang X, Larock RC (2005) Synthesis of fused polycyclic aromatics by palladium-catalyzed annulation of arynes using 2-halobiaryls. J Am Chem Soc 127(45):15716–15717. https://doi.org/10.1021/ja055781o

    Article  CAS  Google Scholar 

  39. Worlikar SA, Larock RC (2009) Synthesis of 9-fluorenylidenes and 9, 10-phenanthrenes through palladium-catalyzed aryne annulation by o-halostyrenes and o-halo allylic benzenes. J Org Chem 74(23):9132–9139. https://doi.org/10.1021/jo9017827

    Article  CAS  Google Scholar 

  40. Lu C, Markina NA, Larock RC (2012) Synthesis of N-acylcarbazoles through palladium-catalyzed aryne annulation of 2-haloacetanilides. J Org Chem 77(24):11153–11160. https://doi.org/10.1021/jo3021727

    Article  CAS  Google Scholar 

  41. Lu C, Dubrovskiy AV, Larock RC (2012) Palladium-catalyzed annulation of arynes by o-halobenzamides: synthesis of phenanthridinones. J Org Chem 77(19):8648–8656. https://doi.org/10.1021/jo3016192

    Article  CAS  Google Scholar 

  42. Dong Y, Liu B, Chen P, Liu Q, Wang M (2014) Palladium-catalyzed C- S activation/aryne insertion/coupling sequence: synthesis of functionalized 2-quinolinones. Angew Chem 126(13):3510–3514. https://doi.org/10.1002/ange.201310340

    Article  Google Scholar 

  43. Feng M, Jiang X (2017) Reactions of arynes involving transition-metal catalysis. Synthesis 49(19):4414–4433. https://doi.org/10.1055/s-0036-1589094

    Article  CAS  Google Scholar 

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Acknowledgments

We are thankful to IISER-Pune, and IIT-Bombay for the spectral analysis. We express our gratitude to Veer Narmad South Gujarat University, Surat and Government Science College, Vankal to provide necessary laboratory facilities. We gratefully acknowledge Bhavik S. Makwana and Prakashsingh M. Chauhan for their suggestion on laboratory setup and reaction mechanism.

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Authors and Affiliations

  1. Department of Chemistry, Government Science College, Vankal, Surat, Gujarat, 394350, India

    Mayur I. Morja

  2. Department of Chemistry, Veer Narmad South Gujarat University, Surat, Gujarat, 395007, India

    Kishor H. Chikhalia

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  1. Mayur I. Morja
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Correspondence to Kishor H. Chikhalia.

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Morja, M.I., Chikhalia, K.H. Palladium(0)-catalyzed aryne annulation: a powerful strategy for the synthesis of thio-bridged compounds. Mol Divers 27, 299–311 (2023). https://doi.org/10.1007/s11030-022-10424-6

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  • DOI: https://doi.org/10.1007/s11030-022-10424-6

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