ACTIVATING EFFECT OF AlCl 3  IN HOMO-COUPLING REACTION OF ACETYLENE COMPOUNDS UNDER THE ACTION OF Mg–Cp 2 ZrCl 2  REAGENT SYSTEMS

I. R. Ramazanov; Рамазанов И. Р.; F. T. Sadykova; Садыкова Ф. Т.; T. P. Zosim; Зосим Т. П.; K. S. Frolova; Фролова К. С.; U. M. Dzhemilev; Джемилев У. М.

doi:10.31857/S2686953522600878

ACTIVATING EFFECT OF AlCl₃ IN HOMO-COUPLING REACTION OF ACETYLENE COMPOUNDS UNDER THE ACTION OF Mg–Cp₂ZrCl₂ REAGENT SYSTEMS

Authors: Ramazanov I.R.¹, Sadykova F.T.¹, Zosim T.P.¹, Frolova K.S.¹, Dzhemilev U.M.²
Affiliations:
1. Institute of Petrochemistry and Catalysis, Ufa Federal Research Center, Russian Academy of Sciences
2. N.D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences
Issue: Vol 512, No 1 (2023)
Pages: 46-51
Section: CHEMISTRY
URL: https://rjmseer.com/2686-9535/article/view/651950
DOI: https://doi.org/10.31857/S2686953522600878
EDN: https://elibrary.ru/HGOXOC
ID: 651950

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Abstract

The activating effect of AlCl₃ in the amount of 10 mol. % in the homo-coupling of alkyl-, phenyl-, and silyl-substituted acetylenes with the Mg–Cp₂ZrCl₂ reagent system was found for the first time. The unique nature of this activation is indicated by the fact that in the presence of 10 mol. % of Lewis acids such as BF₃ ⋅ Et₂O, Me₃SiCl, InCl₃, and SnCl₄, the reaction with 5-decyne does not occur even after 5 h, while in the presence of AlCl₃, homocoupling products are selectively formed in high yield in 10 min at room temperature.

Keywords

alkynes, homo-coupling, cyclometallation, zirconacyclopentadienes, zirconocene

References

Negishi E., Holmes S.J., Tour J.M., Miller J.A., Cederbaum F.E., Swanson D.R., Takahashi T. // J. Am. Chem. Soc. 1989. V. 111. P. 3336–3346. https://doi.org/10.1021/ja00191a035
Negishi E. // Dalton Trans. 2005. P. 827–848. https://doi.org/10.1039/B417134A
Negishi E., Cederbaum F.E., Takahashi T. // Tetrahedron Lett. 1986. V. 27. P. 2829–2832. https://doi.org/10.1016/S0040-4039(00)84653-5
Urrego-Riveros S., Ramirez y Medina I., Duvinage D., Lork E., Sönnichsen F.D., Staubitz A. // Chem. – Eur. J. 2019. V. 25. P. 13318–13328. https://doi.org/10.1002/chem.201902255
Linshoeft J. // Synlett. 2014. V. 25. P. 2671–2672. https://doi.org/10.1055/s-0034-1379317
Rosenthal U., Burlakov V.V. Organometallic chemistry of titanocene and zirconocene complexes with bis (trimethylsilyl) acetylene as the basis for applications in organic synthesis. In: Titanium and Zirconium in Organic Synthesis. Marek I. (Ed.). Wiley-VCH Verlag GmbH & Co. KGaA, 2002. P. 355–389. https://doi.org/10.1002/3527600671.ch10
Sato F., Urabe H., Okamoto S. // Synlett. 2000. V. 2000. P. 753–775. https://doi.org/10.1055/s-2000-6689
Kulinkovich O.G., Sviridov S.V., Vasilevski D.A. // Synthesis. 1991. V. 1991. P. 234. https://doi.org/10.1055/s-1991-26431
Negishi E.-i., Kondakov D.Y., Choueiry Danièle, Kasai K., Takahashi T. // J. Am. Chem. Soc. 1996. V. 118. P. 9577–9588. https://doi.org/10.1021/ja9538039
Dyakonov V.A. Dzhemilev reactions in organic and organometallic synthesis. NOVA Sci. Publ.: New York, 2010. 96 p.
Abakumov G.A., Piskunov A.V., Cherkasov V.K., Fedushkin I.L., Ananikov V.P., Eremin D.B., Gordeev E.G., Beletskaya I.P., Averin A.D., Bochkarev M.N., Trifo-nov A.A., Dzhemilev U.M., D’yakonov V.A., Egorov M.P., Vereshchagin A.N., Syroeshkin M.A., Jouikov V.V., Muzafarov A.M., Anisimov A.A., Arzumanyan A.V., Kono-nevich Yu.N., Temnikov M.N., Sinyashin O.G., Budnikova Yu.H., Burilov A.R., Karasik A.A., Mironov V.F., Storozhenko P.A., Shcherbakova G.I., Trofimov B.A., Amosova S.V., Gusarova N.K., Potapov V.A., Shur V.B., Burlakov V.V., Bogdanov V.S., Andreev M.V. // Russ. Chem. Rev. 2018. V. 87. P. 393–507. https://doi.org/10.1070/RCR4795
Islamov I.I., Makarov A.A., Makarova E.Kh., Yusu-pova A.V., D’yakonov V.A., Dzhemilev U.M. // Russ. Chem. Bull. 2023. V. 72. P. 925–931. https://doi.org/10.1007/s11172-023-3855-1
Dzhemilev U.M., Ibragimov A.G. // Russ. Chem. Rev. 2000. V. 69. P. 121–135. https://doi.org/10.1070/RC2000v069n02ABEH000519
Ramazanov I.R., Kadikova R.N., Amirova A.K., Dzhemilev U.M. // Dokl. Chem. 2020. V. 494. P. 155–158. https://doi.org/10.1134/S0012500820100031
Negishi E.-i. // Chem. – Eur. J. 1999. V. 5. P. 411–420. https://doi.org/10.1002/(SICI)1521-3765(19990201)5:2<411::AID-CHEM411>3.0.CO;2-H
Takahashi T., Li Y. Zirconacyclopentadienes in organic synthesis. In: Titanium and Zirconium in Organic Synthesis. Marek I. (Ed.). Wiley-VCH Verlag GmbH & Co. KGaA, 2002. P. 50–85. https://doi.org/10.1002/3527600671.ch2
Dzhemilev U.M., Ibragimov A.G., D’yakonov V.A., Zinnurova R.A. // Russ. J. Org. Chem. 2007. V. 43. P. 176–180. https://doi.org/10.1134/S1070428007020030
Ramazanov I.R., Kadikova R.N., Amirova A.K., Mozgovoj O.S., Dzhemilev U.M. // RSC Adv. 2021. V. 11. P. 39518–39522. https://doi.org/10.1039/D1RA08268J
Xi Z., Liu X., Lu J., Bao F., Fan H., Li Z., Takahashi T. // J. Org. Chem. 2004. V. 69. P. 8547–8549. https://doi.org/10.1021/jo048940f
Brandsma L., Verkruijsse H.D. Synthesis of acetylenes, allenes, cumulenes: A laboratory manual. Elsevier Science Pub. Co., Amsterdam–New York, 1981. 276 p.