3-Trifluoromethylbenzyne: Precise Orientation in Cycloaddition Reaction Enabled Regioselective Synthesis of Trifluoromethylated Triptycenes

Abstract

The first regioselective addition reactions to 3-trifluoromethylbenzyne are reported. Triple cycloaddition of ynolates to the benzyne provided 1,8,13-tris(trifluoromethyl)triptycenes with high regioselectivity. 1-Trifluoromethyltriptycenes were regioselectively obtained by the Diels–Alder reaction of anthranoxides with the benzyne. These selectivities are attributed to the electron-acceptor nature of the trifluoromethyl group on the benzyne.

Key words

benzynes - trifluoromethyl group - triptycenes - regioselective synthesis - cycloaddition - negative hyperconjugation

Publication History

Received: 14 March 2022

Accepted after revision: 05 April 2022

Accepted Manuscript online:
05 April 2022

Article published online:
31 May 2022

• References

• 1 O’Hagan D. Chem. Soc. Rev. 2008; 37: 308

For reviews, see:
• 2a Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
• 2b Wang J, Sánchez-Roselló M, Aceña JL, Del Pozo C, Sorochinsky AE, Fustero S, Soloshonok VA, Liu H. Chem. Rev. 2014; 114: 2432
• 2c Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
• 3a O’Connor MJ, Boblak KN, Topinka MJ, Kindelin PJ, Briski JM, Zheng C, Klumpp DA. J. Am. Chem. Soc. 2010; 132: 3266
• 3b Charpentier J, Früh N, Togni A. Chem. Rev. 2015; 115: 650
• 4 McClinton MA, McClinton DA. Tetrahedron 1992; 48: 6555
• 5a Berger R, Resnati G, Metrangolo P, Weber E, Hulliger J. Chem. Soc. Rev. 2011; 40: 3496
• 5b Liang T, Neumann CN, Ritter T. Angew. Chem. Int. Ed. 2013; 52: 8214
• 6a Han Y, Meng Z, Ma YX, Chen CF. Acc. Chem. Res. 2014; 47: 2026
• 6b Zhang G, Mastalerz M. Chem. Soc. Rev. 2014; 43: 1934
• 6c Chen C.-F, Han Y. Acc. Chem. Res. 2018; 51: 2093
• 6d Ueberricke L, Mastalerz M. Chem. Rec. 2021; 21: 558

For reviews, see:
• 7a Shindo M. Chem. Soc. Rev. 1998; 27: 367
• 7b Shindo M. Synthesis 2003; 2275
• 7c Shindo M. Tetrahedron 2007; 63: 10
• 7d Shindo M, Matsumoto K. Recent Advances in the Chemistry of Metal Ynolates. In Patai’s Chemistry of Functional Groups, Vol. 1. Zabicky J. John Wiley & Sons, Ltd; Chichester: 2016: 1
• 7e Shindo M, Iwata T. Synlett 2022; 33: 531
• 8a Umezu S, dos Passos Gomes G, Yoshinaga T, Sakae M, Matsumoto K, Iwata T, Alabugin I, Shindo M. Angew. Chem. Int. Ed. 2017; 56: 1298
• 8b Sun J, Iwata T, Shindo M. Chem. Lett. 2020; 49: 1084
• 8c Yoshinaga T, Fujiwara T, Iwata T, Shindo M. Chem. Eur. J. 2019; 25: 13855
• 8d Iwata T, Yoshinaga T, Shindo M. Synlett 2020; 31: 1903
• 8e Iwata T, Kumagai S, Yoshinaga T, Hanada M, Shiota Y, Yoshizawa K, Shindo M. Chem. Eur. J. 2021; 27: 11548
• 9 Iwata T, Shindo M. Chem. Lett. 2021; 50: 39
• 10 Vatsadze SZ, Loginova YD, dos Passos Gomes G, Alabugin IV. Chem. Eur. J. 2017; 23: 3225
• 11 Alabugin IV. Stereoelectronic Effects . John Wiley & Sons, Ltd; Chichester, UK: 2016: 257
• 12 Iwata T, Hyodo M, Fukami T, Shiota Y, Yoshizawa K, Shindo M. Chem. Eur. J. 2020; 26: 8506
• 13a Yamamoto G, Suzuki M, Ōki M. Bull. Chem. Soc. Jpn. 1983; 56: 306
• 13b Bailly F, Cottet F, Schlosser M. Synthesis 2005; 791
• 13c Frantz DK, Linden A, Baldridge KK, Siegel JS. J. Am. Chem. Soc. 2012; 134: 1528
• 13d Nikitin K, Müller-Bunz H, McGlinchey MJ. Organometallics 2013; 32: 6118
• 13e Hornum M, Mulberg MW, Szomek M, Reinholdt P, Brewer JR, Wüstner D, Kongsted J, Nielsen P. J. Org. Chem. 2021; 86: 1471
• 14a Gribble GW, Keavy DJ, Branzt SE, Kelly WJ, Pals MA. Tetrahedron Lett. 1988; 29: 6227
• 14b Yoshida S, Nagai A, Uchida K, Hosoya T. Chem. Lett. 2017; 46: 733
• 15 Matsumoto T, Hosoya T, Katsuki M, Suzuki K. Tetrahedron Lett. 1991; 32: 6735
• 16a Shindo M, Sato Y, Shishido K. Tetrahedron 1998; 54: 2411
• 16b Shindo M, Sato Y, Koretsune R, Yoshikawa T, Matsumoto K, Itoh K, Shishido K. Chem. Pharm. Bull. 2003; 51: 477
• 16c Shindo M, Matsumoto K, Shishido K. Org. Synth. 2007; 84: 11
• 16d Sun J, Yoshiiwa T, Iwata T, Shindo M. Org. Lett. 2019; 21: 6585

For representative examples, see:
• 17a Mallory FB, Mallory CW, Ricker WM. J. Am. Chem. Soc. 1975; 97: 4770
• 17b Mallory FB, Mallory CW, Ricker WM. J. Org. Chem. 1985; 50: 457
• 17c Takemura H, Kotoku M, Yasutake M, Shinmyozu T. Eur. J. Org. Chem. 2004; 2019
• 17d Struble MD, Holl MG, Scerba MT, Siegler MA, Lectka T. J. Am. Chem. Soc. 2015; 137: 11476

For a review, see:
• 17e Hierso J.-C. Chem. Rev. 2014; 114: 4838
• 18a Ikawa T, Kaneko H, Masuda S, Ishitsubo E, Tokiwa H, Akai S. Org. Biomol. Chem. 2015; 13: 520
• 18b Medina JM, Mackey JL, Garg NK, Houk KN. J. Am. Chem. Soc. 2014; 136: 15798
• 19a Gold B, Shevchenko NE, Bonus N, Dudley GB, Alabugin IV. J. Org. Chem. 2012; 77: 75
• 19b Harris T, Alabugin IV. Mendeleev Commun. 2019; 29: 237
• 19c Harris T, dos Passos Gomes G, Ayad S, Clark RJ, Lobodin VV, Tuscan M, Hanson K, Alabugin IV. Chem 2017; 3: 629

For representative examples, see:
• 20a Pieper U, Walter S, Klingebiel U, Stalke D. Angew. Chem. Int. Ed. Engl. 1990; 29: 209
• 20b Yamazaki T, Haga J, Kitazume T, Nakamura S. Chem. Lett. 1991; 20: 2171
• 20c Shinohara N, Haga J, Yamazaki T, Kitazume T, Nakamura S. J. Org. Chem. 1995; 60: 4363
• 20d Egami H, Usui Y, Kawamura S, Shimizu R, Nagashima S, Sodeoka M. J. Fluorine Chem. 2015; 179: 121
• 21 CCDC 2154694 (distal-11), CCDC 2154695 (13a), and CCDC 2154697 (13d) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
• 22 Iwata T, Kawano R, Fukami T, Shindo M. Chem. Eur. J. 2022; 28: e202104160
• 23 Kofron WG, Baclawski LM. J. Org. Chem. 1976; 41: 1879