Alumina-Promoted Copper-Catalyzed Hydroboration of Alkynes

Abstract

Alumina was found to activate Cu(I) catalysts in hydroboration of alkynes. This allowed to develop a simple and efficient protocol for hydroboration of alkynes with B₂Pin₂ using inexpensive CuCl/PPh₃ catalytic system. The approach does not require moisture-sensitive activators and stepwise preparation of ‘activated’ Cu complex. The developed conditions were applied to the preparation of β-styrylboronates from terminal and internal alkynes with excellent regio- and stereoselectivity. The procedure can also be extended to other terminal alkynes by the appropriate choice of ligand.

Key words

alumina - copper - hydroboration - alkynes - vinylboronic esters - stereoselective synthesis

Publikationsverlauf

Eingereicht: 15. November 2023

Angenommen nach Revision: 02. Januar 2024

Accepted Manuscript online:
02. Januar 2024

Artikel online veröffentlicht:
31. Januar 2024

• References

• 1a Carreras J, Caballero A, Pérez PJ. Chem. Asian J. 2019; 14: 329
• 1b Hall DG. Boronic Acids: Preparation, Applications in Organic Synthesis and Medicine. Wiley; New York: 2006

For selected reviews, see:
• 2a Beletskaya IP, Alonso F, Tyurin V. Coord. Chem. Rev. 2019; 385: 137
• 2b Lennox AJ. J, Lloyd-Jones GC. Chem. Soc. Rev. 2013; 43: 412
• 2c Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
• 3a Berthon G, Hayashi T. In Catalytic Asymmetric Conjugate Reactions . Cordova A. Wiley; New York: 2010: 1-70
• 3b Hayashi T. Synlett 2001; 879
• 3c Hayashi T, Yamasaki K. Chem. Rev. 2003; 103: 2829
• 4a Marques C, Brandão P. Catalysts 2023; 13: 1022
• 4b Wu P, Givskov M, Nielsen TE. Chem. Rev. 2019; 119: 11245
• 4c Petasis NA. In Multicomponent Reactions . Zhu J, Bienaymé H. Wiley; New York: 2005: 199-223
• 4d Petasis NA, Akritopoulou I. Tetrahedron Lett. 1993; 34: 583

For reviews, see:
• 5a Vijayan A, Rao DN, Radhakrishnan KV, Lam PY. S, Das P. Synthesis 2021; 53: 805
• 5b Chen J.-Q, Li J.-H, Dong Z.-B. Adv. Synth. Catal. 2020; 362: 3311
• 5c West MJ, Fyfe JW. B, Vantourout JC, Watson AJ. B. Chem. Rev. 2019; 119: 12491

For selected examples, see:
• 5d Tkachuk VM, Lukianov OO, Vovk MV, Gillaizeau I, Sukach VA. Beilstein J. Org. Chem. 2020; 16: 2304
• 5e Steemers L, van Maarseveen JH. Org. Biomol. Chem. 2019; 17: 2103
• 5f Motornov V, Latyshev GV, Kotovshchikov YN, Lukashev NV, Beletskaya IP. Adv. Synth. Catal. 2019; 361: 3306
• 5g Steemers L, Wijsman L, van Maarseveen JH. Adv. Synth. Catal. 2018; 360: 4241
• 5h Huang F, Quach TD, Batey RA. Org. Lett. 2013; 15: 3150

For recent examples, see:
• 6a Zhao C.-G, Du C, Guo Z, Li W, Han J, Xie J. Angew. Chem. Int. Ed. 2023; 62: e202312414
• 6b Gosak K, Časar Z. Tetrahedron Lett. 2023; 64: 154804
• 6c Jang WJ, Woo J, Yun J. Angew. Chem. Int. Ed. 2021; 60: 4614
• 6d Lee H, Lee S, Yun J. ACS Catal. 2020; 10: 2069
• 6e Zhang Y, Han B, Zhu S. Angew. Chem. Int. Ed. 2019; 58: 13860
• 6f Bera S, Hu X. Angew. Chem. Int. Ed. 2019; 58: 13854
• 6g Corless VB, Holownia A, Foy H, Mendoza-Sanchez R, Adachi S, Dudding T, Yudin AK. Org. Lett. 2018; 20: 5300
• 7a Brown HC, Gupta SK. J. Am. Chem. Soc. 1975; 97: 5249
• 7b Tucker CE, Davidson J, Knochel P. J. Org. Chem. 1992; 57: 3482

For recent achievements in TM-free hydroboration with HBPin, see:
• 7c Ton NN. H, Mai BK, Nguyen TV. J. Org. Chem. 2021; 86: 9117
• 7d Yan D, Wu X, Xiao J, Zhu Z, Xu X, Bao X, Yao Y, Shen Q, Xue M. Org. Chem. Front. 2019; 6: 648
• 7e Bisai MK, Yadav S, Das T, Vanka K, Sen SS. Chem. Commun. 2019; 55: 11711
• 7f Liu J, Wu C, Hu T, Yang W, Xie Y, Shi Y, Liu Q, Shao Y, Zhang F. J. Org. Chem. 2022; 87: 3442
• 7g Li J, An M, Gao Z, Guo Y, Liu H, Zhao P, Bi X, Shi E, Xiao J. RSC Adv. 2022; 12: 16530
• 7h Magre M, Maity B, Falconnet A, Cavallo L, Rueping M. Angew. Chem. Int. Ed. 2019; 58: 7025

For reviews on TM-catalyzed hydroboration, see:
• 8a Geier SJ, Vogels CM, Melanson JA, Westcott SA. Chem. Soc. Rev. 2022; 51: 8877
• 8b Trost BM, Ball ZT. Synthesis 2005; 853
• 8c Beletskaya I, Pelter A. Tetrahedron 1997; 53: 4957
• 9a Wang Y, Li Y, Wang L, Ding S, Song L, Zhang X, Wu Y.-D, Sun J. J. Am. Chem. Soc. 2023; 145: 2305
• 9b Ding H, Gao W, Yu T, Wang Z, Gou F, Ding S. J. Org. Chem. 2022; 87: 1526
• 9c Fiorito D, Mazet C. ACS Catal. 2018; 8: 9382
• 10a Martínez-Bascuñana A, Núñez-Rico JL, Carreras L, Vidal-Ferran A. ACS Catal. 2023; 13: 10447
• 10b Lyu Y, Toriumi N, Iwasawa N. Org. Lett. 2021; 23: 9262
• 10c Pereira S, Srebnik M. Tetrahedron Lett. 1996; 37: 3283
• 11a Parsutkar MM, Bhunia S, Majumder M, Lalisse RF, Hadad CM, RajanBabu TV. J. Am. Chem. Soc. 2023; 145: 7462
• 11b Jia J, Wu T, Fu Y, Hu Z, Tang H, Pan Y, Huang F. Adv. Synth. Catal. 2022; 364: 1873
• 11c Bołt M, Żak P. RSC Adv. 2022; 12: 18572
• 11d Bergamaschi E, Teskey CJ. Tetrahedron Lett. 2022; 98: 153813
• 11e Yang Y, Zeng J.-H, Zhan Z.-P. Org. Chem. Front. 2021; 8: 2537
• 11f González MJ, Bauer F, Breit B. Org. Lett. 2021; 23: 8199
• 11g Chen X, Cheng Z, Lu Z. ACS Catal. 2019; 9: 4025
• 12a Gorgas N, Stöger B, Veiros LF, Kirchner K. ACS Catal. 2018; 8: 7973
• 12b Khan A, Asiri AM, Kosa SA, Garcia H, Grirrane A. J. Catal. 2015; 329: 401
• 12c Greenhalgh MD, Jones AS, Thomas SP. ChemCatChem 2015; 7: 190
• 13 Zhang G, Zeng H, Zheng S, Neary MC, Dub PA. ACS Catal. 2022; 12: 5425
• 14 Liu J, Xie Y, Wu C, Shao Y, Zhang F, Shi Y, Liu Q, Chen J. Org. Chem. Front. 2021; 8: 3802
• 15 Mandal S, Verma PK, Geetharani K. Chem. Commun. 2018; 54: 13690

For selected examples, see:
• 16a Lou Y, Wang J, Gong G, Guan F, Lu J, Wen J, Zhang X. Chem. Sci. 2020; 11: 851
• 16b Zhu G, Kong W, Feng H, Qian Z. J. Org. Chem. 2014; 79: 1786
• 16c Lipshutz BH, Bošković ŽV, Aue DH. Angew. Chem. Int. Ed. 2008; 47: 10183
• 17a Takahashi K, Ishiyama T, Miyaura N. Chem. Lett. 2000; 29: 982
• 17b Takahashi K, Ishiyama T, Miyaura N. J. Organomet. Chem. 2001; 625: 47
• 17c Lee J.-E, Kwon J, Yun J. Chem. Commun. 2008; 733

For reviews, see:
• 17d Hemming D, Fritzemeier R, Westcott SA, Santos WL, Steel PG. Chem. Soc. Rev. 2018; 47: 7477
• 17e Barbeyron R, Benedetti E, Cossy J, Vasseur J.-J, Arseniyadis S, Smietana M. Tetrahedron 2014; 70: 8431

For hydroborations of alkynes with B₂Pin₂, catalyzed by other TMs, see:
• 18a Bhawar R, Saini S, Nagaraju DH, Bose SK. Adv. Synth. Catal. 2023; 365: 584
• 18b Xu L, Dong Z, Zhang Q, Deng N, Li S.-Y, Xu H.-J. J. Org. Chem. 2022; 87: 14879
• 19a Bidal YD, Lazreg F, Cazin CS. J. ACS Catal. 2014; 4: 1564
• 19b Stavber G, Časar Z. Appl. Organomet. Chem. 2013; 27: 159
• 19c Wei R.-J, You P.-Y, Duan H, Xie M, Xia R.-Q, Chen X, Zhao X, Ning G.-H, Cooper AI, Li D. J. Am. Chem. Soc. 2022; 144: 17487
• 19d Zhong M, Gagné Y, Hope TO, Pannecoucke X, Frenette M, Jubault P, Poisson T. Angew. Chem. Int. Ed. 2021; 60: 14498
• 20a Fujihara T, Semba K, Terao J, Tsuji Y. Catal. Sci. Technol. 2014; 4: 1699
• 20b Semba K, Shinomiya M, Fujihara T, Terao J, Tsuji Y. Chem. Eur. J. 2013; 19: 7125
• 20c Semba K, Fujihara T, Terao J, Tsuji Y. Chem. Eur. J. 2012; 18: 4179
• 20d Roy S, Mishra A, Sekhar Pati S, Behera M, Prakash Das J. Asian J. Org. Chem. 2023; 12: e202200505
• 21a Zhang P, Meijide Suárez J, Driant T, Derat E, Zhang Y, Ménand M, Roland S, Sollogoub M. Angew. Chem. Int. Ed. 2017; 56: 10821
• 21b Jang H, Zhugralin AR, Lee Y, Hoveyda AH. J. Am. Chem. Soc. 2011; 133: 7859

For reviews, see:
• 22a Li B, Liang H, Vignesh A, Zhou X, Liu Y, Ke Z. Molecules 2023; 28: 2252
• 22b Chen J.-B, Whiting A. Synthesis 2018; 50: 3843
• 22c Yun J. Asian J. Org. Chem. 2013; 2: 1016
• 23a Ting SI, Snelson DW, Huffman TR, Kuroo A, Sato R, Shenvi RA. J. Am. Chem. Soc. 2023; 145: 20634
• 23b Zheng C, Xie T, He H, Gao S. Org. Lett. 2021; 23: 469
• 23c Linne Y, Bonandi E, Tabet C, Geldsetzer J, Kalesse M. Angew. Chem. Int. Ed. 2021; 60: 6938
• 23d Xie T, Zheng C, Chen K, He H, Gao S. Angew. Chem. Int. Ed. 2020; 59: 4360
• 23e Zhang Q, Zhang F.-M, Zhang C.-S, Liu S.-Z, Tian J.-M, Wang S.-H, Zhang X.-M, Tu Y.-Q. Nat. Commun. 2019; 10: 2507
• 23f Meng Z, Fürstner A. J. Am. Chem. Soc. 2019; 141: 805
• 23g Yoshida H, Takemoto Y, Takaki K. Chem. Commun. 2014; 50: 8299
• 23h Hesse MJ, Butts CP, Willis CL, Aggarwal VK. Angew. Chem. Int. Ed. 2012; 51: 12444

For reviews, see:
• 24a Innocenti R, Lenci E, Trabocchi A. Tetrahedron Lett. 2020; 61: 152083
• 24b Shimizu Y, Kanai M. Tetrahedron Lett. 2014; 55: 3727

For representative examples, see:
• 24c Zhao H, Lin Y, Jiang M, Su B. Chem. Sci. 2023; 14: 7897
• 24d Gao Y, Kim N, Mendoza SD, Yazdani S, Faria Vieira A, Liu M, Kendrick A, Grotjahn DB, Bertrand G, Jazzar R, Engle KM. ACS Catal. 2022; 12: 7243
• 24e Li Z, Sun J. Org. Lett. 2021; 23: 3706
• 24f Cheng T, Liu B, Wu R, Zhu S. Chem. Sci. 2022; 13: 7604
• 24g Suliman AM. Y, Ahmed E.-AM. A, Gong T.-J, Fu Y. Org. Lett. 2021; 23: 3259
• 24h Baumann JE, Lalic G. Angew. Chem. Int. Ed. 2022; 61: e202206462

For representative procedures, see:
• 25a Feng C, Wang H, Xu L, Li P. Org. Biomol. Chem. 2015; 13: 7136
• 25b Alfaro R, Parra A, Alemán J, García Ruano JL, Tortosa M. J. Am. Chem. Soc. 2012; 134: 15165
• 26a Beletskaya IP, Nenajdenko VG. Angew. Chem. Int. Ed. 2019; 58: 4778
• 26b Nájera C, Beletskaya IP, Yus M. Chem. Soc. Rev. 2019; 48: 4515
• 26c Beletskaya IP, Nájera C, Yus M. Russ. Chem. Rev. 2020; 89: 250
• 27 Activator-free Cu-catalyzed hydroboration usually requires specific catalysts and prolonged heating, see, e.g.: Tsai H, Madasu M, Huang MH. Chem. Eur. J. 2019; 25: 1300
• 28 Chan T.-L, Fong S, Li Y, Man T.-O, Poon C.-D. J. Chem. Soc., Chem. Commun. 1994; 1771
• 29a Yamawaki J, Kawate T, Ando T, Hanafusa T. Bull. Chem. Soc. Jpn. 1983; 56: 1885
• 29b Blass BE. Tetrahedron 2002; 58: 9301
• 30 Weinstock LM, Stevenson JM, Tomellin SA, Pan S.-H, Utne T, Jobson RB, Reinhold DF. Tetrahedron Lett. 1986; 27: 3845
• 31a Roy CD, Brown HC. J. Organomet. Chem. 2007; 692: 784
• 31b Oka N, Yamada T, Sajiki H, Akai S, Ikawa T. Org. Lett. 2022; 24: 3510

Cu(OAc)₂ is known to catalyze reaction of B₂Pin₂ with alkynes:
• 32a Huang J, Li X, Wen H, Ouyang L, Luo N, Liao J, Luo R. ACS Omega 2021; 6: 11740
• 32b Han X, Hu J, Chen C, Yuan Y, Shi Z. Chem. Commun. 2019; 55: 6922
• 32c Yoshida H, Kawashima S, Takemoto Y, Okada K, Ohshita J, Takaki K. Angew. Chem. Int. Ed. 2012; 51: 235
• 32d Yoshida H, Kageyuki I, Takaki K. Org. Lett. 2013; 15: 952
• 33a Hosoya H, Misal Castro LC, Sultan I, Nakajima Y, Ohmura T, Sato K, Tsurugi H, Suginome M, Mashima K. Org. Lett. 2019; 21: 9812
• 33b Hayrapetyan D, Khalimon AY. Chem. Asian J. 2020; 15: 2575
• 34 Ho HE, Asao N, Yamamoto Y, Jin T. Org. Lett. 2014; 16: 4670
• 35 Reid WB, Spillane JJ, Krause SB, Watson DA. J. Am. Chem. Soc. 2016; 138: 5539
• 36 Gioia B, Arnaud A, Radix S, Walchshofer N, Doléans-Jordheim A, Rocheblave L. Tetrahedron Lett. 2020; 61: 151596
• 37 Zhao J, Niu Z, Fu H, Li Y. Chem. Commun. 2014; 50: 2058