Design of a Chiral Secondary Amine Ligand for Copper-Catalyzed anti-Selective Henry Reaction

Abstract

A series of chiral binaphthyl-containing diphenylethylene­diamine (binaph-dpen) ligands was designed and synthesized for the copper-catalyzed asymmetric Henry reaction. The N-monobenzyl (S)-binaph-(R,R)-dpen ligand, with a secondary amine portion, promoted the Cu(OAc)₂-catalyzed Henry reaction with excellent enantioselectivity in an anti-selective manner.

Key words

asymmetric catalysis - diastereoselectivity - copper - ligands - nitroaldol

• References and Notes


Reviews on catalytic asymmetric Henry reactions:
• 1a Shibasaki M, Gröger H In Comprehensive Asymmetric Catalysis III . Jacobsen EN, Pfaltz A, Yamamoto H. Springer-Verlag; Berlin-Heidelberg: 1999. Chap. 29.3
• 1b Palomo C, Oiarbide M, Mielgo A. Angew. Chem. Int. Ed. 2004; 43: 5442
• 1c Palomo C, Oiarbide M, Laso A. Eur. J. Org. Chem. 2007; 2561
• 1d Blay G, Hernández-Olmos V, Pedro JR. Synlett 2011; 1195
• 2a Sasai H, Suzuki T, Arai S, Arai T, Shibasaki M. J. Am. Chem. Soc. 1992; 114: 4418
• 2b Arai T, Yamada YM. A, Yamamoto N, Sasai H, Shibasaki M. Chem. Eur. J. 1996; 2: 1368
• 2c For a lanthanum-containing catalyst, see: Tur F, Saá JM. Org. Lett. 2007; 9: 5079
• 3a Trost BM, Yeh VS. C. Angew. Chem. Int. Ed. 2002; 41: 861
• 3b Palomo C, Oiarbide M, Laso A. Angew. Chem. Int. Ed. 2005; 44: 3881
• 3c Zheng B, Wang M, Li Z, Bian Q, Mao J, Li S, Liu S, Wang M, Zhong J, Guo H. Tetrahedron: Asymmetry 2011; 22: 1156
• 4a Kogami Y, Nakajima T, Ashizawa T, Kezuka S, Ikeno T, Yamada T. Chem. Lett. 2004; 33: 614
• 4b Park J, Lang K, Abboud KA, Hong S. J. Am. Chem. Soc. 2008; 130: 16484
• 4c Wei Y.-L, Yang K.-F, Li F, Zheng Z.-J, Xu Z, Xu L.-W. RSC Adv. 2014; 4: 37859

For selected examples of copper catalysis, see:
• 5a Christensen C, Juhl K, Jørgensen KA. Chem. Commun. 2001; 2222
• 5b Evans DA, Seidel D, Rueping M, Lam HW, Shaw JT, Downey CW. J. Am. Chem. Soc. 2003; 125: 12692
• 5c Maheswaran H, Prasanth KL, Krishna GG, Ravikumar K, Sridhar B, Kantam ML. Chem. Commun. 2006; 4066
• 5d Ma K, You J. Chem. Eur. J. 2007; 13: 1863
• 5e Bandini M, Piccinelli F, Tommasi S, Umani-Ronchi A, Ventrici C. Chem. Commun. 2007; 616
• 5f Qin B, Xiao X, Liu X, Huang J, Wen Y, Feng X. J. Org. Chem. 2007; 72: 9323
• 5g Bandini M, Benaglia M, Sinisi R, Tommasi S, Umani-Ronchi A. Org. Lett. 2007; 9: 2151
• 5h Xiong Y, Wang F, Huang X, Wen Y, Feng X. Chem. Eur. J. 2007; 13: 829
• 5i Arai T, Yokoyama N, Yanagisawa A. Chem. Eur. J. 2008; 14: 2052
• 5j Constable EC, Zhang G, Housecroft CE, Neuburger M, Schaffner S, Woggon W.-D. New J. Chem. 2009; 33: 1064
• 5k Jin W, Li X, Huang Y, Wu F, Wan B. Chem. Eur. J. 2010; 16: 8259
• 5l Blay G, Hernandez-Olmos V, Pedro JR. Synlett 2011; 1195
• 5m Kodama K, Sugawara K, Hirose T. Chem. Eur. J. 2011; 17: 13584
• 5n Zhou Z.-M, Li Z.-H, Hao X.-Y, Zhang J, Dong X, Liu Y.-Q, Sun W.-W, Cao D, Wang J.-L. Org. Biomol. Chem. 2012; 10: 2113
• 5o Cheng H.-G, Lu L.-Q, Wang T, Chen J.-R, Xiao W.-J. Chem. Commun. 2012; 48: 5596
• 5p Angulo B, Garcia JI, Herrerias CI, Mayoral JA, Minana AC. J. Org. Chem. 2012; 77: 5525
• 5q Qin D.-D, Lai W.-H, Hu D, Chen Z, Wu A.-A, Ruan Y.-P, Zhou Z.-H, Chen H.-B. Chem. Eur. J. 2012; 18: 10515
• 5r Leighty MW, Shen B, Johnston JN. J. Am. Chem. Soc. 2012; 134: 15233
• 5s Dai Q, Rana NK, Zhao JC.-G. Org. Lett. 2013; 15: 2922
• 5t Zhou Y, Zhu Y, Yan S, Gong Y. Angew. Chem. Int. Ed. 2013; 52: 10265
• 5u Holmquist M, Blay G, Munoz MC, Pedro JR. Org. Lett. 2014; 16: 1204
• 5v Scharnagel D, Prause F, Kaldun J, Haase RG, Breuning M. Chem. Commun. 2014; 50: 6623
• 5w Das A, Choudhary MK, Kureshy RI, Roy T, Khan NH, Abdi SH. R, Bajaj HC. ChemPlusChem 2014; 79: 1138
• 6 Choudary BM, Ranganath KV. S, Pal U, Kantam ML, Sreedhar B. J. Am. Chem. Soc. 2005; 127: 13167
• 7a Kowalczyk R, Sidorowicz L, Skarzewski J. Tetrahedron: Asymmetry 2007; 18: 2581
• 7b Zulauf A, Mellah M, Schulz E. J. Org. Chem. 2009; 74: 2242

For selected examples of organocatalysis, see:
• 8a Corey EJ, Zhang F.-Y. Angew. Chem. Int. Ed. 1999; 38: 1931
• 8b Ooi T, Doda K, Maruoka K. J. Am. Chem. Soc. 2003; 125: 2054
• 8c Marcelli T, van der Haas RN. S, van Maarseveen JH, Hiemstra H. Angew. Chem. Int. Ed. 2006; 45: 929
• 8d Mandal T, Samanta S, Zhao C.-G. Org. Lett. 2007; 9: 943
• 8e Palacio C, Connon SJ. Org. Lett. 2011; 13: 1298
• 8f Kitagaki S, Ueda T, Mukai C. Chem. Commun. 2013; 49: 4030
• 8g Nakayama Y, Hidaka Y, Ito K. Synlett 2013; 24: 883
• 8h Breugst M, Houk KN. J. Org. Chem. 2014; 79: 6302
• 8i Vlatkovic M, Bernardi L, Otten E, Feringa BL. Chem. Commun. 2014; 50: 7773

Selected examples of syn-selective catalytic asymmetric nitro­aldol reaction, see:
• 9a Sasai H, Tokunaga T, Watanabe S, Suzuki T, Itoh N, Shibasaki M. J. Org. Chem. 1995; 60: 7388
• 9b Sohtome Y, Hashimoto Y, Nagasawa K. Eur. J. Org. Chem. 2006; 2894
• 9c Sohtome Y, Takemura N, Takada K, Takagi R, Iguchi T, Nagasawa K. Chem. Asian J. 2007; 2: 1150
• 9d Yoshimoto J, Sandoval CA, Saito S. Chem. Lett. 2008; 37: 1294
• 9e Kim HY, Oh K. Org. Lett. 2009; 11: 5682
• 9f Cheng L, Dong J, You J, Gao G, Lan J. Chem. Eur. J. 2010; 16: 6761
• 9g Jin W, Li X, Wan B. J. Org. Chem. 2011; 76: 484
• 9h Chougnet A, Zhang G, Liu K, Haeussinger D, Kaegi A, Allmendinger T, Woggon W.-D. Adv. Synth. Catal. 2011; 353: 1797
• 9i White JD, Shaw S. Org. Lett. 2012; 14: 6270
• 9j Qin D.-D, Yu W, Zhou J.-D, Zhang Y.-C, Ruan Y.-P, Zhou Z.-H, Chen H.-B. Chem. Eur. J. 2013; 19: 16541

For selected examples of anti-selective catalytic asymmetric nitroaldol reaction, see:
• 10a Uraguchi D, Sakaki S, Ooi T. J. Am. Chem. Soc. 2007; 129: 12392
• 10b Nitabaru T, Kumagai N, Shibasaki M. Tetrahedron Lett. 2008; 49: 272
• 10c Handa S, Nagawa K, Sohtome Y, Matsunaga S, Shibasaki M. Angew. Chem. Int. Ed. 2008; 47: 3230
• 10d Sohtome Y, Kato Y, Handa S, Aoyama N, Nagawa K, Matsunaga S, Shibasaki M. Org. Lett. 2008; 10: 2231
• 10e Blay G, Domingo LR, Hernández-Olmos V, Pedro JR. Chem. Eur. J. 2008; 14: 4725
• 10f Ube H, Terada M. Bioorg. Med. Chem. Lett. 2009; 19: 3895
• 10g Nitabaru T, Nojiri A, Kobayashi M, Kumagai N, Shibasaki M. J. Am. Chem. Soc. 2009; 131: 13860
• 10h Noole A, Lippur K, Metsala A, Lopp M, Kanger T. J. Org. Chem. 2010; 75: 1313
• 10i Blay G, Hernández-Olmos V, Pedro JR. Org. Lett. 2010; 12: 3058
• 10j Uraguchi D, Nakamura S, Ooi T. Angew. Chem. Int. Ed. 2010; 49: 7562
• 10k Ji YQ, Qi G, Judeh ZM. A. Tetrahedron: Asymmetry 2011; 22: 2065
• 10l Ji YQ, Qi G, Judeh ZM. A. Eur. J. Org. Chem. 2011; 4892
• 10m Lang K, Park J, Hong S. Angew. Chem. Int. Ed. 2012; 51: 1620
• 10n Boobalan R, Lee G.-H, Chen C. Adv. Synth. Catal. 2012; 354: 2511
• 10o Yao L, Wei Y, Wang P, He W, Zhang S. Tetrahedron 2012; 68: 9119
• 10p Xu K, Lai G, Zha Z, Pan S, Chen H, Wang Z. Chem. Eur. J. 2012; 18: 12357
• 10q Ogawa T, Kumagai N, Shibasaki M. Angew. Chem. Int. Ed. 2013; 52: 6196
• 10r Hashimoto K, Kumagai N, Shibasaki M. Org. Lett. 2014; 16: 3496
• 11 Arai T, Watanabe M, Fujiwara A, Yokoyama N, Yanagisawa A. Angew. Chem. Int. Ed. 2006; 45: 5978
• 12 Arai T, Watanabe M, Yanagisawa A. Org. Lett. 2007; 9: 3595
• 13a Arai T, Takashita R, Endo Y, Watanabe M, Yanagisawa A. J. Org. Chem. 2008; 73: 4903
• 13b Arai T, Taneda Y, Endo Y. Chem. Commun. 2010; 46: 7936
• 14a Gao J.-X, Ikariya T, Noyori R. Organometallics 1996; 15: 1087
• 14b Ikariya T, Murata K, Noyori R. Org. Biomol. Chem. 2006; 4: 393
• 14c Ikariya T, Gridnev ID. Chem. Rec. 2009; 9: 106
• 14d Jiang Y, Jiang Q, Zhang X. J. Am. Chem. Soc. 1998; 120: 3817
• 15 Da Silva ET, Lima EL. S. Tetrahedron Lett. 2003; 44: 3621
• 16 Diastereoselective Henry Reaction To Give 2-Nitro-1-(2-nitrophenyl)propan-1-ol; General Procedure: The catalyst was prepared by complex formation between ligand L8 (6.4 mg, 0.011 mmol) with Cu(OAc)₂·H₂O (2.0 mg, 0.01 mmol) in anhydrous CH₂Cl₂ (1.0 mL) under Ar. After stirring overnight at r.t., the solvent was removed under reduced pressure and the residue was dissolved in EtOH (0.4 mL). To the resulting clear, blue solution were added nitroethane (147 μL, 2 mmol), 2-ethynylpiridine (2.0 μL, 0.02 mmol), and the aldehyde (0.2 mmol) under Ar. After stirring for the appropriate time, the reaction mixture was quenched with 1 M HCl and extracted with CH₂Cl₂. The organic layer was washed with brine and then dried with sodium sulfate. After removal of the solvent under reduced pressure, the residue was purified by silica gel column chromatography (n-hexane–EtOAc) to afford the adduct. ¹H NMR (400 MHz, CDCl₃): δ = 8.10 (dd, J = 1.4, 8.5 Hz, 1 H, anti), 8.02 (d, J = 8.2 Hz, 0.17 H, syn), 7.94 (d, J = 7.3 Hz, 1 H, anti), 7.70–7.76 (m, 1.34 H, syn/anti), 7.52–7.57 (m, 1.17 H, syn/anti), 6.10 (d, J = 2.5 Hz, 1 H, anti), 5.73 (d, J = 6.6 Hz, 0.17 H, syn), 4.97–5.03 (m, 1.17 H, syn/anti), 3.17 (br, 1.28 H, syn/anti), 1.57 (d, J = 7.1 Hz, 0.51 H, syn), 1.54 (d, J = 6.9 Hz, 3 H, anti). ¹³C NMR (100 MHz, CDCl₃): δ = 12.0 (anti), 16.4 (syn), 69.2 (anti), 70.6 (syn), 84.7 (anti), 87.5 (syn), 125.0 (syn), 125.2 (anti), 128.8 (syn), 129.3 (anti), 129.4 (anti), 129.7 (syn), 134.0 (syn), 134.1 (anti), 147.1 (anti), 148.08 (syn).