Catalytic Asymmetric Synthesis of Atropisomeric Quinolines through the Friedländer Reaction

Abstract

A phosphoric acid catalyzed atroposelective Friedländer reaction was developed in which acetylacetone and a variety of 2′-substituted 2-aminobenzophenones were successfully employed to give optically active biaryl quinolines in good yields and with high enantioselectivities.

Key words

Friedländer reaction - atroposelectivity - quinolines - phosphoric acids - acetylacetone

• References and Notes

• 1 Christie GH, Kenner J. J. Chem. Soc., Trans. 1922; 121: 614

For review, see:
• 2a Brunel JM. corrigendum: Chem. Rev. 2005; 105: 857; Chem. Ref. 2005, 105, 4233
• 2b Brunel JM. Chem. Rev. 2007; 107: PR1
• 2c Genet J.-P, Ayad T, Ratovelomanana-Vidal V. Chem. Rev. 2014; 114: 2824
• 2d Miyashita A, Yasuda A, Takaya H, Toriumi K, Ito T, Souchi T, Noyori R. J. Am. Chem. Soc. 1980; 102: 7932
• 2e Akutagawa S. Appl. Catal., A 1995; 128: 171
• 2f Kumobayashi H, Miura T, Sayo N, Saito T, Zhang X. Synlett 2001; 1055
• 2g Strong JG. PharmaChem 2003; 2: 20
• 3a Bringmann G, Gulder T, Gulder TA. M, Breuning M. Chem. Rev. 2011; 111: 563
• 3b Smyth JE, Butler NM, Keller PA. Nat. Prod. Rep. 2015; 32: 1562
• 4a Clayden J, Moran WJ, Edwards PJ, LaPlante SR. Angew. Chem. Int. Ed. 2009; 48: 6398
• 4b LaPlante SR, Edwards PJ, Fader LD, Jakalian A, Hucke O. ChemMedChem 2011; 6: 505
• 4c Zask A, Murphy J, Ellestad GA. Chirality 2013; 25: 265

For selected works, see:
• 5a Wu Y.-L, Ferroni F, Pieraccini S, Schweizer WB, Frank BB, Spada GP, Diederich F. Org. Biomol. Chem. 2012; 10: 8016
• 5b Zhu Y.-Y, Wu X.-D, Gu S.-X, Pu L. J. Am. Chem. Soc. 2019; 141: 175

For a review, see:
• 5c Pu L. Acc. Chem. Res. 2012; 45: 150

For recent reviews on the synthesis of axially chiral biaryls, see:
• 6a Baudoin O. Eur. J. Org. Chem. 2005; 4223
• 6b Bringmann G, Price Mortimer AJ, Keller PA, Gresser MJ, Garner J, Breuning M. Angew. Chem. Int. Ed. 2005; 44: 5384
• 6c Wallace TW. Org. Biomol. Chem. 2006; 4: 3197
• 6d Tanaka K. Chem. Asian J. 2009; 4: 508
• 6e Bringmann G, Menche D. Acc. Chem. Res. 2001; 34: 615
• 6f Wencel-Delord J, Panossian A, Leroux FR, Colobert F. Chem. Soc. Rev. 2015; 44: 3418
• 6g Ma G, Sibi MP. Chem. Eur. J. 2015; 21: 11644
• 6h Kumarasamy E, Raghunathan R, Sibi MP, Sivaguru J. Chem. Rev. 2015; 115: 11239
• 6i Yang H, Yang X, Tang W. Tetrahedron 2016; 72: 6143
• 6j Loxq P, Manoury E, Poli R, Deydier E, Labande A. Coord. Chem. Rev. 2016; 308: 131
• 6k Renzi P. Org. Biomol. Chem. 2017; 15: 4506
• 6l Zilate B, Castrogiovanni A, Sparr C. ACS Catal. 2018; 8: 2981
• 6m Link A, Sparr C. Chem. Soc. Rev. 2018; 47: 3804
• 6n Wang Y.-B, Tan B. Acc. Chem. Res. 2018; 51: 534
• 6o Metrano AJ, Miller SJ. Acc. Chem. Res. 2019; 52: 199

For reviews on asymmetric C–H functionalization, see:
• 7a Giri R, Shi B.-F, Engle KM, Maugel N, Yu J.-Q. Chem. Soc. Rev. 2009; 38: 3242
• 7b Yang L, Huang H. Catal. Sci. Technol. 2012; 2: 1099
• 7c Engle KM, Yu J.-Q. J. Org. Chem. 2013; 78: 8927
• 7d Wencel-Delord J, Colobert F. Chem. Eur. J. 2013; 19: 14010
• 7e Zheng C, You S.-L. RSC Adv. 2014; 4: 6173
• 7f Pedroni J, Cramer N. Chem. Commun. 2015; 51: 17647
• 7g Newton CG, Wang S.-G, Oliveira CC, Cramer N. Chem. Rev. 2017; 117: 8908
• 7h Saint-Denis TG, Zhu R.-Y, Chen G, Wu Q.-F, Yu J.-Q. Science 2018; 359: eaao4798

For a book, see:
• 7i Asymmetric Functionalization of C–H Bonds . You S.-L. Royal Society of Chemistry; Cambridge: 2015
• 8 Wang J, Chen M.-W, Ji Y, Hu S.-B, Zhou Y.-G. J. Am. Chem. Soc. 2016; 138: 10413
• 9 Miyaji R, Asano K, Matsubara S. Chem. Eur. J. 2017; 23: 9996

For some representative work on the construction of axial chirality involving organocatalytic annulation, see:
• 10a Link A, Sparr C. Angew. Chem. Int. Ed. 2014; 53: 5458
• 10b Fäseke VC, Sparr C. Angew. Chem. Int. Ed. 2016; 55: 7261
• 10c Zhang L, Zhang J, Ma J, Cheng D.-J, Tan B. J. Am. Chem. Soc. 2017; 139: 1714
• 10d Wang Y.-B, Zheng S.-C, Hu Y.-M, Tan B. Nat. Commun. 2017; 8: 15489
• 10e Zhao C, Guo D, Munkerup K, Huang K.-W, Li F, Wang J. Nat. Commun. 2018; 9: 611
• 10f Liu Y, Wu X, Li S, Xue L, Shan C, Zhao Z, Yan H. Angew. Chem. Int. Ed. 2018; 57: 6491
• 11a Kang G, Luo Z, Liu C, Gao H, Wu Q, Wu H, Jiang J. Org. Lett. 2013; 15: 4738
• 11b Gao H, Luo Z, Ge P, He J, Zhou F, Zheng P, Jiang J. Org. Lett. 2015; 17: 5962
• 11c Wang N, Liu H, Gao H, Zhou J, Zheng L, Li J, Xiao H.-P, Li X, Jiang J. Org. Lett. 2019; 21: 6684
• 12 During the preparation of this manuscript, Cheng et. al. reported a chiral phosphoric acid and achiral amine co-catalyzed Friedländer reaction; see: Shao Y.-D, Dong M.-M, Wang Y.-A, Cheng P.-M, Wang T, Cheng D.-J. Org. Lett. 2019; 21: 4831
• 13a Li L, Seidel D. Org. Lett. 2010; 12: 5064
• 13b Ren L, Lei T, Gong L.-Z. Chem. Commun. 2011; 47: 11683
• 13c Bañón-Caballero A, Guillena G, Nájera C. J. Org. Chem. 2013; 78: 5349
• 14 Gheewala CD, Collins BE, Lambert TH. Science 2016; 351: 961
• 15 Phosphoric-Acid-Catalyzed Asymmetric Friedländer Reaction; General Procedure A Schlenk tube was charged with the appropriate 2-aminobenzophenone 1 (1 equiv, 0.1 mmol), acetylacetone (2; 5 equiv, 0.5 mmol), catalyst Cat.5 (0.1 equiv, 10% mmol), powdered 5 Å MS (50 mg), and anhyd PhCN (0.5 mL). The resulting mixture was stirred at rt for 12 h and then at 120 °С for an additional 8 h. When the reaction was complete, the mixture was purified by flash column chromatography [silica gel, PE–EtOAc (8:1 to 6:1)]. 1-[2-Methyl-5-(3-{2-[4-(trifluoromethyl)phenyl]ethyl}phenyl)quinolin-3-yl]ethanone (4a) Yellow liquid; yield: 39.9 mg (92%; ee 88%); [α]_D ²⁷ +5.6 (c 0.01, EtOAc). HPCL [Daicel Chiralpak AD-H, hexane–i-PrOH (98:2), flow rate: 0.7 mL/min, λ = 254 nm, 25°С]: t _R (major) = 11.40 min; t _R (minor) = 12.42 min. ¹H NMR (500 MHz, CDCl₃): δ = 8.09 (d, J = 8.4 Hz, 1 H), 7.76–7.68 (m, 1 H), 7.46 (t, J = 7.3 Hz, 1 H), 7.42–7.32 (m, 5 H), 7.25 (d, J = 9.4 Hz, 1 H), 7.19 (d, J = 7.4 Hz, 1 H), 6.89 (d, J = 8.0 Hz, 2 H), 2.81–2.60 (m, 2 H), 2.71 (s, 3 H), 2.66–2.60 (m, 1 H), 2.56–2.49 (m, 1 H), 2.08 (s, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 205.01, 153.54, 147.37, 145.26, 143.11, 139.86, 135.16, 134.42, 130.22, 130.08, 129.38, 129.28, 128.93, 128.53, 126.62, 126.23, 125.98, 125.46, 125.20, 125.17, 125.14, 125.11, 36.10, 34.64, 31.90, 23.85. HRMS (Bruker micrOTOF-QII): m/z [M + H]⁺ calcd for C₂₇H₂₃F₃NO: 434.1726; found: 434.1743.1-[2,7-Dimethyl-5-(3-{2-[4-(trifluoromethyl)phenyl]ethyl}phenyl)quinolin-3-yl]ethanone (4b) Yellow liquid; yield: 38.9 mg (87%; ee 93%); [α]_D ²⁷ +16.4 (c 0.01, EtOAc); HPLC [Daicel Chiralpak AD-H, hexane–i-PrOH (98:2), flow rate 0.7 mL/min, λ = 254 nm, 25 °С]: t _R (major) = 9.18 min, t _R (minor) = 11.06 min. ¹H NMR (500 MHz, CDCl₃): δ = 7.86 (s, 1 H), 7.45 (t, J = 7.5 Hz, 1 H), 7.40 (d, J = 7.4 Hz, 1 H), 7.35–7.31 (m, 3 H), 7.18 (t, J = 7.6 Hz, 2 H), 7.12 (d, J = 8.5 Hz, 1 H), 6.89 (d, J = 8.0 Hz, 2 H), 2.81–2.71 (m, 2 H), 2.69 (s, 3 H), 2.66–2.60 (m, 1 H), 2.58–2.51 (m, 1 H), 2.54 (s, 3 H), 2.07 (s, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 205.21, 153.48, 147.61, 145.30, 142.95, 140.73, 139.81, 134.64, 134.42, 130.06, 129.38, 129.19, 128.84, 128.56, 127.98, 126.19, 125.66, 125.17, 125.14, 125.11, 125.08, 123.42, 36.13, 34.62, 31.96, 23.85, 21.71. HRMS (Bruker micrOTOF-QII): m/z [M + H]⁺ calcd for C₂₈H₂₅F₃NO: 448.1883; found: 448.1879.
• 16 CCDC 1957624 contains the supplementary crystallographic data for compound (S,R)-5. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.