Fused λ⁵-Phosphinines: Design, Syntheses, and Properties

Dedicated to Professor Masahiro Murakami on the occasion of his retirement

Abstract

Synthesis of several heterocycle-fused λ⁵-phosphinines through intramolecular cyclization is described. The incorporation of a heteroatom affected their photophysical properties through perturbation of the LUMO level, which is in good contrast to the HOMO-based tuning by the C-4 substituent. The C-3-substituent-based property tuning provides a new guide to designing phosphinine-based fluorophores.

Key words

phosphinine - heteroaromatics - fluorescence - cyclization - coupling

Publication History

Received: 24 October 2022

Accepted: 15 November 2022

Accepted Manuscript online:
15 November 2022

Article published online:
01 December 2022

• References and Notes


For reviews, see:
• 1a Lavis LD, Raines RT. ACS Chem. Biol. 2014; 9: 855
• 1b Li X, Gao X, Shi W, Ma H. Chem. Rev. 2014; 114: 590
• 1c Kobayashi H, Ogawa M, Alford R, Choyke PL, Urano Y. Chem. Rev. 2010; 110: 2620

For reviews, see:
• 2a Mathey F. Chem. Rev. 1988; 88: 429
• 2b Matano Y, Imahori H. Org. Biomol. Chem. 2009; 7: 1258
• 2c Duffy MP, Delaunay W, Bouit P.-A, Hissler M. Chem. Soc. Rev. 2016; 45: 5296
• 2d Shameem MA, Orthaber A. Chem. Eur. J. 2016; 22: 10718
• 2e Hibner-Kulicka P, Joule JA, Skalik J, Bałczewski P. RSC Adv. 2017; 7: 9194

For selected syntheses of 6-membered phosphorus heterocycles, see:
• 3a Nagahora N, Goto S, Inatomi T, Tokumaru H, Matsubara K, Shioji K, Okuma K. J. Org. Chem. 2018; 83: 6373
• 3b Fukazawa A, Suda S, Taki M, Yamaguchi E, Grzybowski M, Sato Y, Higashiyama T, Yamaguchi S. Chem. Commun. 2016; 52: 1120
• 3c Savateev A, Vlasenko Y, Shtil N, Kostyuk A. Eur. J. Inorg. Chem. 2016; 628
• 3d Matveeva ED, Vinogradov DS, Podrugina TA, Nekipelova TD, Mironov AV, Gleiter R, Zefirov NS. Eur. J. Org. Chem. 2015; 7324
• 3e Heim U, Pritzkow H, Fleischer U, Grützmacher H, Sanchez M, Reáu R, Bertrand G. Chem. Eur. J. 1996; 2: 68
• 4 Hashimoto N, Umano R, Ochi Y, Shimahara K, Nakamura J, Mori S, Ohta H, Watanabe Y, Hayashi M. J. Am. Chem. Soc. 2018; 140: 2046
• 5a Ledos N, Sangchai T, Knysh I, Bousquet MH. E, Manzhi P, Cordier M, Tondelier D, Geffroy B, Jacquemin D, Bouit P.-A, Hissler M. Org. Lett. 2022; 24: 6869
• 5b Delouche T, Caytan E, Cordier M, Roisnel T, Taupier G, Molard Y, Vanthuyne N, Le Guennic B, Hissler M, Jacquemin D, Bouit P.-A. Angew. Chem. Int. Ed. 2022; 61: e202205548
• 5c Tang X, Balijapalli U, Okada D, Karunathilaka BS. B, Senevirathne CA. M, Lee Y.-T, Feng Z, Sandanayaka AS. D, Matsushima T, Adachi C. Adv. Funct. Mater. 2021; 31: 2104529
• 5d Karunathilaka BS. B, Balijapalli U, Senevirathne CA. M, Yoshida S, Esaki Y, Goushi K, Matsushima T, Sandanayaka AS. D, Adachi C. Nat. Commun. 2020; 11: 4926
• 5e Karunathilaka BS. B, Balijapalli U, Senevirathne CA. M, Esaki Y, Goushi K, Matsushima T, Sandanayaka AS. D, Adachi C. Adv. Funct. Mater. 2020; 30: 2001078
• 5f Pfeifer G, Chahdoura F, Papke M, Weber M, Szucs R, Geffroy B, Tondelier D, Nyulaszi L, Hissler M, Mueller C. Chem. Eur. J. 2020; 26: 10534
• 5g Huang J, Tarábek J, Kulkarni R, Wang C, Dračínský M, Smales GJ, Tian Y, Ren S, Pauw BR, Resch-Genger U, Bojdys MJ. Chem. Eur. J. 2019; 25: 12342
• 6 Representative Experimental Procedure for 2b Aminophosphinine 3b (234 mg, 0.60 mmol) was dissolved in EtOH (24 mL), and 1 M HCl aq. (2 mL) and MnO₂ (102 mg, 1.20 mmol) were added at r.t. After 5 min, the mixture was filtered and concentrated. The residue was purified by a column chromatography on silica gel (eluent: AcOEt/CHCl₃/n-hexane = 1/2/6) to give 2b as a yellow solid (220 mg, 77%). Characterization data for 2b, the other synthetic procedures, and analytical data for each compound including cyclization precursors are available in the Supporting Information.
• 7 Zhang T, Deng G, Li H, Liu B, Tan Q, Xu B. Org. Lett. 2018; 20: 5439
• 8 CCDC 2214502 (2a), 2214503 (2b), 2214506 (2c), 2214506 (2d), 2214509 (2e), and 2214510 (3a′) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures