Zirconium-Mediated Synthesis of Multi-substituted Dibenzosilole and Benzonaphthosilole Derivatives

Abstract

In this study, a new zirconium-mediated cycloaddition for preparing dibenzosilole derivatives was developed using silicon-bridged diynes and electron-withdrawing alkynes as starting materials. The preparation of silicon-bridged diynes from 1-bromide-2-iodobenzene, terminal alkynes, and dimethyldichlorosilane was also studied. Unlike in the previous synthesis methods, much higher yields of electron-withdrawing group-substituted dibenzosilole derivatives were obtained. In addition, a new synthesis strategy for preparing benzonaphthosilole derivatives using internal alkynes, 1,4-dibromobenzene, and electron-withdrawing alkynes as starting materials is proposed. Compared with previous methods, alkyl, phenyl, and electron-withdrawing groups can be successfully introduced onto aromatic rings, and the positions of these substituents can be easily controlled. The cycloaddition reactions for dibenzosilole and benzonaphthosilole derivatives are highly efficient one-pot processes, and the raw materials are available and easily prepared. Using these new methods, a series of novel multi-substituted dibenzonsilole and benzonaphthosilole derivatives were obtained effectively.

Keywords

Zirconium-mediated reactions / Dibenzosilole derivatives / Benzonaphthosilole derivatives / Multi-substitution

References

[1] Hong YN, Lam JWY, Tang BZ. Aggregation-induced emission. Chem Soc Rev, 2011, 40: 5361-5388.

[2] Tamao K, Uchida M, Izumizawa T, et al. Silole derivatives as efficient electron transporting materials. J Am Chem Soc, 1996, 118: 11974-11975.

[3] Quan CY, Nie H, Hu RR, et al. A silole-based efficient electroluminescent material with good electron-transporting potential. Chin J Chem, 2015, 33: 842-846.

[4] Anthony JE, Facchetti A, Heeney M, et al. N-type organic semiconductors in organic electronics. Adv Mater, 2010, 22: 3876-3892.

[5] Erlik O, Unlu NA, Hizalan G, et al. Silafluorene-based polymers for electrochromic and polymer solar cell applications. J Polym Sci Pol Chem, 2015, 53: 1541-1547.

[6] Duan CH, Cai WZ, Huang F, et al. Novel silafluorene-based conjugated polymers with pendant acceptor groups for high performance solar cells. Macromolecules, 2010, 43: 5262-5268.

[7] Yuan MJ, Yang PY, Durban MM, et al. Low bandgap polymers based on silafluorene containing multifused heptacylic arenes for photovoltaic applications. Macromolecules, 2012, 45: 5934-5940.

[8] Wang E, Li C, Zhuang WL, et al. High-efficiency red and green light-emitting polymers based on a novel wide bandgap poly(2,7-silafluorene). J Mater Chem, 2008, 18: 797-801.

[9] Yang J, Aschemeyer S, Martinez HP, et al. Hollow silica nanospheres containing a silafluorene-fluorene conjugated polymer for aqueous TNT and RDX detection. Chem Commun, 2010, 46: 6804-6806.

[10] Ouyang KB, Liang Y, Xi ZF. Construction of benzosiloles, six- and eight-membered silacyclic skeletons, via a Pd-catalyzed intramolecular Mizoroki–Heck Reaction of vinylsilanes. Org Lett, 2012, 14(17): 4572-4575.

[11] Li LC, Xiang JF, Xu CH. Synthesis of novel ladder bis-silicon-bridged p-terphenyls. Org Lett, 2007, 9(23): 4877-4879.

[12] Murai M, Matsumoto K, Okada R, et al. Rhodium-catalyzed dehydrogenative germylation of C-H bonds: new entry to unsymmetrically functionalized 9-germafluorenes. Org Lett, 2014, 16: 6492-6495.

[13] Xu L, Zhang S, Li PF. Synthesis of silafluorenes and silaindenes via silyl radicals from arylhydrosilanes: intramolecular cyclization and intermolecular annulations with alkynes. Org Chem Front, 2015, 2: 459-463.

[14] Murata M, Takizawa M, Sasaki H, et al. Synthesis of dibenzosiloles via Platinum-catalyzed intramolecular dehydrogenative cyclization of 2-(Dialkylsilyl)biaryls. Chem Lett, 2016, 45: 857-859.

[15] Hudrlik PF, Dai DH, Hudrlik AM. Reactions of dilithiobutadienes with monochlorosilanes: observation of facile loss of organic groups from silicon. J Organomet Chem, 2006, 691: 1257-1264.

[16] Matsuda T, Kadowaki S, Goya T, et al. Synthesis of silafluorenes by Iridium-catalyzed [2 + 2+2] cycloaddition of silicon-bridged diynes with alkynes. Org Lett, 2007, 9(1): 133-136.

[17] Murai M, Okada R, Asako S, et al. Rhodium-catalyzed silylative and germylative cyclization with dehydrogenation leading to 9-sila- and 9-germafluorenes: a combined experimental and computational mechanistic study. Chem Eur J, 2017, 23: 10861-10870.

[18] Ureshino T, Yoshida T, Kuninobu Y, et al. Rhodium-catalyzed synthesis of silafluorene derivatives via cleavage of silicon–hydrogen and carbon–hydrogen bonds. J Am Chem Soc, 2010, 132: 14324-14326.

[19] Murai M, Okada R, Nishiyama A, et al. Synthesis and properties of sila[n]helicenes via dehydrogenative silylation of C–H bonds under Rhodium catalysis. Org Lett, 2016, 18: 4380-4383.

[20] Seri T, Qu HM, Zhou LS, et al. Substituent effects in the preparation of naphthacenes by the coupling reaction of diyne-derived zirconacyclopentadienes with tetraiodobenzene. Chem Asian J, 2008, 3: 388-392.

[21] Li S, Qu HM, Zhou LS, et al. Zirconium-mediated selective synthesis of 1,2,4,5-tetrasubstituted benzenes from two silyl-substituted alkynes and one internal alkyne. Org Lett, 2009, 11(15): 3318-3321.

[22] Wang H, Li JQ, Zhou LS, et al. Palladium-catalyzed synthesis of 1,2,3,4-tetraalkyl-1,4-diarylbutadienes by cross-coupling of zirconacyclopentadienes with aryl iodides. Chin Chem Lett, 2015, 26: 1303-1306.

[23] Arndt S, Hansmann MM, Motloch P, et al. Intramolecular anti-phosphinoauration of alkynes: an FLP-motivated approach to stable aerated phosphindolium complexes. Chem Eur J, 2017, 23: 2542-2547.

[24] Just G, Singh R. The synthesis of 11-13-membered diacetylenic and 18-membered tetraacetylenic ring systems. Tetrahedron Lett, 1987, 28(48): 5981-5984.

[25] Duhovic S, Dinca M. Synthesis and electrical properties of covalent organic frameworks with heavy chalcogens. Chem Mater, 2015, 27: 5487-5490.

[26] Takahashi T, Xi ZF, Yamazaki A, et al. Cycloaddition reaction of zirconacyclopentadienes to alkynes: highly selective formation of benzene derivatives from three different alkynes. J Am Chem Soc, 1998, 120: 1672-1680.

[27] Li JQ, Zhang JQ, Qu HM, et al. Zirconium-mediated selective synthesis of 1,4-dialkyl(aryl)-hexa-substituted benzenes from two silyl-substituted alkynes and one internal alkyne. Chem Res Chin Univ, 2016, 32(3): 366-372.