Palladium-Catalyzed Coupling of Biphenyl-2-yl Trifluoromethanesulfonates with Dibromomethane to Access Fluorenes

Abstract

A facile and efficient method has been developed for the synthesis of fluorenes by Pd-catalyzed C–H alkylation of biphenyl-2-yl trifluoromethanesulfonates. The trifluoromethanesulfonates are more readily available and more environmentally benign than biphenyl iodides, and are advantageous substrates for traceless directing-group-assisted C–H activation. The reaction generates C,C-palladacycles as the key intermediates that form two C(sp²)–C(sp³) bonds through reaction with CH₂Br₂. The reaction tolerates various functional groups, permitting easy access to a range of fluorene derivatives.

Key words

palladium catalysis - fluorenes - C–H bond activation - biphenyl triflates - dibromomethane

Publikationsverlauf

Eingereicht: 16. Januar 2022

Angenommen nach Revision: 11. Februar 2022

Accepted Manuscript online:
11. Februar 2022

Artikel online veröffentlicht:
10. März 2022

• References and Notes

• 1a C–H Activation. In Topics in Current Chemistry, Vol. 292. HYu J.-Q, Shi Z. Springer; Heidelberg: 2010
• 1b Zhang Y, Shi G, Yu J.-Q. 2014; 3: 1101
• 1c Miao J, Ge H. Eur. J. Org. Chem. 2015; 2015: 7859
• 1d Song G, Li X. Acc. Chem. Res. 2015; 48: 1007
• 1e Gensch T, Hopkinson MN, Glorius F, Wencel-Delord J. Chem. Soc. Rev. 2016; 45: 2900
• 1f Moselage M, Li J, Ackermann L. ACS Catal. 2016; 6: 498
• 1g Baudoin O. Acc. Chem. Res. 2017; 50: 1114
• 1h He J, Wasa M, Chan KS. L, Shao Q, Yu J.-Q. Chem. Rev. 2017; 117: 8754
• 1i Yang Y, Lan J, You J. Chem. Rev. 2017; 117: 8787
• 1j Liu C, Yuan J, Gao M, Tang S, Li W, Shi R, Lei A. Chem. Rev. 2015; 115: 12138
• 1k Dong Z, Ren Z, Thompson SJ, Xu Y, Dong G. Chem. Rev. 2017; 117: 9333
• 1l Wu Z, Cheng C, Zhang Y. Youji Huaxue 2021; 41: 2155
• 1m Zhao Q, Meng G, Nolan SP, Szostak M. Chem. Rev. 2020; 120: 1981
• 1n Gandeepan P, Müller T, Zell D, Cera G, Warratz S, Ackermann L. Chem. Rev. 2019; 119: 2192
• 1o Segawa Y, Maekawa T, Itami K. Angew. Chem. Int. Ed. 2015; 54: 66
• 2a Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
• 2b Engle KM, Mei T.-S, Wasa M, Yu J.-Q. Acc. Chem. Res. 2012; 45: 788
• 2c Chen Z, Wang B, Zhang J, Yu W, Liu Z, Zhang Y. Org. Chem. Front. 2015; 2: 1107
• 2d Liao G, Zhang T, Lin Z.-K, Shi B.-F. Angew. Chem. Int. Ed. 2020; 59: 19773
• 2e Rej S, Ano Y, Chantani N. Chem. Rev. 2020; 120: 1788
• 3a Vyhivskyi O, Kudashev A, Miyakoshi T, Baudoin O. Chem. Eur. J. 2021; 27: 1231
• 3b Cao L, Hua Y, Cheng H.-G, Zhou Q. Org. Chem. Front. 2021; 8: 3883
• 4a Chaumontet M, Piccardi R, Audic N, Hitce J, Peglion J.-L, Clot E, Baudoin O. J. Am. Chem. Soc. 2008; 130: 15157
• 4b Albicker MR, Cramer N. Angew. Chem. Int. Ed. 2009; 48: 9139
• 4c Rousseaux S, Davi M, Sofack-Kreutzer J, Pierre C, Kefalidis CE, Clot E, Fagnou K, Baudoin O. J. Am. Chem. Soc. 2010; 132: 10706
• 4d Shintani R, Otomo H, Ota K, Hayashi T. J. Am. Chem. Soc. 2012; 134: 7305
• 4e Deng R, Huang Y, Ma X, Li G, Zhu R, Wang B, Kang Y.-B, Gu Z. J. Am. Chem. Soc. 2014; 136: 4472
• 4f Gao D.-W, Yin Q, Gu Q, You S.-L. J. Am. Chem. Soc. 2014; 136: 4841
• 4g Yan J.-X, Li H, Liu X.-W, Shi J.-L, Wang X, Shi Z.-J. Angew. Chem. Int. Ed. 2014; 53: 4945
• 4h Dyker G. Angew. Chem., Int. Ed. Engl. 1992; 31: 1023
• 4i Dyker G. Angew. Chem., Int. Ed. Engl. 1994; 33: 103
• 4j Wu Z, Ma D, Zhou B, Ji X, Ma X, Wang X, Zhang Y. Angew. Chem. Int. Ed. 2017; 56: 12288
• 4k Gutiérrez-Bonet Á, Juliá-Hernández F, de Luis B, Martin R. J. Am. Chem. Soc. 2016; 138: 6384
• 4l Lu A, Ji X, Zhou B, Wu Z, Zhang Y. Angew. Chem. Int. Ed. 2018; 57: 3233
• 4m Lv W, Wen S, Yu J, Cheng G. Org. Lett. 2018; 20: 4984
• 4n Li W, Chen W, Zhou B, Xu Y, Deng G, Liang Y, Yang Y. Org. Lett. 2019; 21: 2718
• 4o Tan B, Bai L, Ding P, Liu J, Wang Y, Luan X. Angew. Chem. Int. Ed. 2019; 58: 1474
• 4p Cheng C, Zhu Q, Zhang Y. Chem. Commun. 2021; 57: 9700
• 4q Cheng C, Zhang Y. Org. Lett. 2021; 23: 5772
• 4r Wu Z, Jiang H, Zhang Y. Chem. Sci. 2021; 12: 8531
• 4s Wu Z, Wei F, Wan B, Zhang Y. J. Am. Chem. Soc. 2021; 143: 4524
• 4t Wan B, Lu Z, Wu Z, Cheng C, Zhang Y. Org. Lett. 2021; 23: 1269
• 4u Gu Y, Sun X, Wan B, Lu Z, Zhang Y. Chem. Commun. 2020; 56: 10942
• 4v Majdecki M, Niedbała P, Jurczak J. ChemistrySelect 2020; 5: 6424
• 4w Majdecki M, Tyszka-Gumkowska A, Jurczak J. Org. Lett. 2020; 22: 8687
• 4x Majdecki M, Grodek P, Jurczak J. J. Org. Chem. 2021; 86: 995
• 5 Chen D, Shi G, Jiang H, Zhang Y. Org. Lett. 2016; 18: 2130
• 6a Cornella J, Zarate C, Martin R. Chem. Soc. Rev. 2014; 43: 8081
• 6b Qiu Z, Li C. Chem. Rev. 2020; 120: 10454
• 6c Li B.-J, Yu D.-G, Sun C.-L, Shi Z.-J. Chem. Eur. J. 2011; 17: 1728
• 6d So CM, Kwong FY. Chem. Soc. Rev. 2011; 40: 4963
• 6e Kozhushkov S, Potukuchi HK, Ackermann L. Catal. Sci. Technol. 2013; 3: 562
• 7a Wang J, Zhao J, Gong H. Chem. Commun. 2017; 53: 10180
• 7b Kang K, Huang L, Weix DJ. J. Am. Chem. Soc. 2020; 142: 10634
• 7c Fillion E, Trépanier V. É, Heikkinen JJ, Remorova AA, Carson RJ, Goll JM, Seed A. Organometallics 2009; 28: 3518
• 7d Neely JM, Bezdek MJ, Chirik PJ. ACS Cent. Sci. 2016; 2: 935
• 8a Cai S.-L, Li Y, Yang C, Sheng J, Wang X.-S. ACS Catal. 2019; 9: 10299
• 8b Ferguson DM, Rudolph SR, Kalyani D. ACS Catal. 2014; 4: 2395
• 8c Clemenceau A, Thesmar P, Gicquel M, Le Flohic A, Baudoin O. J. Am. Chem. Soc. 2020; 142: 15355
• 8d Pedroni J, Cramer N. Chem. Commun. 2015; 51: 17647
• 8e Cruz AC. F, Miller ND, Willis MC. Org. Lett. 2007; 9: 4391
• 8f Uryu M, Hiraga T, Koga Y, Saito Y, Murakami K, Itami K. Angew. Chem. Int. Ed. 2020; 59: 6551
• 9a Shi G, Chen D, Jiang H, Zhang Y, Zhang Y. Org. Lett. 2016; 18: 2958
• 9b Pan S, Jiang H, Zhang Y, Chen D, Zhang Y. Org. Lett. 2016; 18: 5192
• 9c Yang S, Zhang Y. Org. Lett. 2021; 23: 7746
• 9d Cheng C, Zuo X, Tu D, Wan B, Zhang Y. Chem. Commun. 2021; 57: 2939
• 9e Cheng C, Tu D, Zuo X, Wu Z, Wan B, Zhang Y. Org. Lett. 2021; 23: 1239
• 9f Shao C, Zhou B, Wu Z, Ji X, Zhang Y. Adv. Synth. Catal. 2018; 360: 887
• 9g Ma D, Shi G, Wu Z, Ji X, Zhang Y. J. Org. Chem. 2018; 83: 1065
• 9h Wan B, Zhang Y. Synthesis 2021; 53: 3299

By other groups:
• 9i Tobisu M, Imoto S, Ito S, Chatani N. J. Org. Chem. 2010; 75: 4835
• 9j Tan B, Liu L, Zheng H, Cheng T, Zhu D, Yang X, Luan X. Chem. Sci. 2020; 11: 10198
• 9k Liu X, Sheng H, Zhou Y, Song Q. Chem. Commun. 2020; 56: 1665
• 9l Xu S, Chen R, Fu Z, Zhou Q, Zhang Y, Wang J. ACS Catal. 2017; 7: 1993
• 9m Larock RC, Tian Q. J. Org. Chem. 1998; 63: 2002
• 9n Larock RC, Doty MJ, Tian Q, Zenner JM. J. Org. Chem. 1997; 62: 7536
• 9o Campo MA, Larock RC. Org. Lett. 2000; 2: 3675
• 9p Campo MA, Larock RC. J. Org. Chem. 2002; 67: 5616
• 9q Masselot D, Charmant JP. H, Gallagher T. J. Am. Chem. Soc. 2006; 128: 694
• 9r Huang L, Chen L.-P, Du Y, Fang M.-Y, Wang B.-Q, Feng C, Xiang S.-K. Org. Lett. 2021; 23: 7535
• 9s Zhang M, Deng W, Sun M, Zhou L, Deng G, Liang Y, Yang Y. Org. Lett. 2021; 23: 5744
• 9t Wang X.-C, Wang H.-R, Xu X, Zhao D. Eur. J. Org. Chem. 2021; 3039
• 9u Fang M.-Y, Chen L.-P, Huang L, Fang D.-M, Chen X.-Z, Wang B.-Q, Feng C, Xiang S.-K. J. Org. Chem. 2021; 86: 9096
• 9v Zhu M.-H, Zhang X.-W, Usman M, Cong H, Liu W.-B. ACS Catal. 2021; 11: 5703
• 9w Tang B.-C, He C.-H, Chen X.-L, Ma J.-T, Wang M, Wu Y.-D, Wu A.-X. Chem. Commun. 2021; 57: 121
• 9x Li W, Xiao G, Deng G, Liang Y. Org. Chem. Front. 2018; 5: 1488
• 10a Fleckenstein A, Plenio H. Chem. Eur. J. 2007; 13: 2701
• 10b Belogi G, Zhu T, Boons G.-J. Tetrahedron Lett. 2000; 41: 6969
• 10c Miyatake K, Byungchan B, Watanabe M. Polym. Chem. 2011; 2: 1919
• 10d Poriel C, Sicard L, Rault-Berthelot J. Chem. Commun. 2019; 55: 14238
• 10e Morgan LR, Thangaraj K, LeBlanc B, Rodgers A, Wolford LT, Hooper CL, Fan D, Jursic BS. J. Med. Chem. 2003; 46: 4552
• 10f Beutler U, Fuenfschilling PC, Steinkemper A. Org. Process Res. Dev. 2007; 11: 341
• 11a Kim J, Ohk Y, Park SH, Jung Y, Chang S. Chem. Asian J. 2011; 6: 2040
• 11b Fu WC, Kwong FY. Chem. Sci. 2020; 11: 1411
• 11c Morimoto K, Itoh M, Hirano K, Satoh T, Shibata Y, Tanaka K, Miura M. Angew. Chem. Int. Ed. 2012; 51: 5359
• 11d Lustosa DM, Cieslik P, Hartmann D, Bruckhoff T, Rudolph M, Rominger F, Hashmi AS. K. Org. Chem. Front. 2019; 6: 1655
• 12a Zhou A.-H, Pan F, Zhu C, Ye L.-W. Chem. Eur. J. 2015; 21: 10278
• 12b Hwang SJ, Kim HJ, Chang S. Org. Lett. 2009; 11: 4588
• 12c Liu S, Roch LM, Allemann O, Xu J, Vanthuyne N, Baldridge KK, Siegel JS. J. Org. Chem. 2018; 83: 3979
• 12d Hirano M, Kawazu S, Komine N. Organometallics 2014; 33: 1921
• 12e Chen H, Hurhangee M, Nikolka M, Zhang W, Kirkus M, Neophytou M, Cryer SJ, Harkin D, Hayoz P, Abdi-Jalebi M, McNeill CR, Sirringhaus H, McCulloch I. Adv. Mater. (Weinheim, Ger.) 2017; 29: 1702523
• 12f Dong C.-G, Hu Q.-S. Angew. Chem. Int. Ed. 2006; 45: 2289
• 12g Hsiao C.-H, Lin Y.-K, Liu C.-J, Wu T.-C, Wu Y.-T. Adv. Synth. Catal. 2010; 352: 3267
• 13 Cámpora J, Palma P, del Río D, López JA, Valerga P. Chem. Commun. 2004; 1490
• 14 Fluorenes 3; General Procedure A 25 mL Schlenk tube equipped with a stirrer bar was charged with the appropriate biphenyl-2-yl triflate 1 (0.2 mmol, 1.0 equiv), CH₂Br₂ (1.4 mmol, 7.0 equiv), Pd(OAc)₂ (0.02 mmol, 0.1 equiv), KHCO₃ (0.4 mmol, 2.0 equiv), KOAc (0.6 mmol, 3.0 equiv), i-PrOH (0.2 mL), and DMF (2.0 mL). The tube was then frozen with liquid N₂ and exchanged with N₂ to remove air. The mixture was then stirred at 60 °C for 12 h until the reaction was complete. The resulting mixture was diluted with EtOAc and washed with sat. aq NaCl (3×). The organic phase was collected and dried (MgSO₄), and the residue was purified by column chromatography (silica gel, petroleum ether/EtOAc). 9H-Fluorene (3a) White solid (80%). ¹H NMR (400 MHz, CDCl₃): δ = 7.81 (d, J = 7.5 Hz, 2 H), 7.56 (d, J = 7.4 Hz, 2 H), 7.39 (t, J = 7.3 Hz, 2 H), 7.32 (td, J = 7.3, 0.9 Hz, 2 H), 3.92 (s, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 143.2, 141.7, 126.7, 126.7, 125.0, 119.8, 36.9. HRMS (ESI-TOF): m/z [M + H]⁺ calcd for C₁₃H₁₁: 167.0855; found: 167.0865. 2-Methyl-9H-fluorene (3b) White solid (56%). ¹H NMR (400 MHz, CDCl₃): δ = 7.76 (d, J = 7.5 Hz, 1 H), 7.68 (d, J = 7.7 Hz, 1 H), 7.53 (d, J = 7.4 Hz, 1 H), 7.39–7.35 (m, 2 H), 7.31–7.25 (m, 1 H), 7.20 (d, J = 7.7 Hz, 1 H), 3.87 (s, 2 H), 2.44 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 143.5, 143.0, 141.8, 139.0, 136.5, 127.5, 126.6, 126.2, 125.7, 124.9, 119.6, 119.5, 36.8, 21.6. HRMS (ESI-TOF): m/z [M – H]⁺ calcd for C₁₄H₁₁: 179.0855; found: 179.0866. 3-Methyl-9H-fluorene (3c) White solid (70%). ¹H NMR (400 MHz, CDCl₃): δ = 7.78 (d, J = 7.5 Hz, 1 H), 7.62 (s, 1 H), 7.54 (d, J = 7.4 Hz, 1 H), 7.44 (d, J = 7.6 Hz, 1 H), 7.38 (t, J = 7.4 Hz, 1 H), 7.34–7.27 (m, 1 H), 7.14 (d, J = 7.6 Hz, 1 H), 3.87 (s, 2 H), 2.47 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 143.6, 141.8, 141.7, 140.3, 136.3, 127.6, 126.6, 126.5, 125.0, 124.7, 120.4, 119.70, 36.5, 21.5. HRMS (ESI-TOF): m/z [M – H]⁺ calcd for C₁₄H₁₁: 179.0855; found: 179.0873. 4-Methyl-9H-fluorene (3d) White solid (44%). ¹H NMR (400 MHz, CDCl₃): δ = 7.94 (d, J = 7.7 Hz, 1 H), 7.58 (d, J = 7.4 Hz, 1 H), 7.40 (t, J = 7.9 Hz, 2 H), 7.32 (td, J = 7.4, 0.7 Hz, 1 H), 7.22 (t, J = 7.4 Hz, 1 H), 7.16 (d, J = 7.4 Hz, 1 H), 3.92 (s, 2 H), 2.74 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 143.6, 143.6, 142.7, 139.8, 133.0, 129.0, 126.6, 126.4, 126.0, 124.9, 123.1, 122.4, 37.1, 21.1. HRMS (ESI-TOF): m/z [M – H]⁺ calcd for C₁₄H₁₁: 179.0855; found: 179.0880.