CC BY-ND-NC 4.0 · Synlett 2019; 30(04): 401-404
DOI: 10.1055/s-0037-1610408
letter
Copyright with the author

Design of New Amino Tf-Amide Organocatalysts: Environmentally Benign Approach to Asymmetric Aldol Synthesis

Hyo-Jun Lee
a  Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan   Email: maruoka@kuchem.kyoto-u.ac.jp
,
Natarajan Arumugam
b  Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia
,
Abdulrahman I. Almansour
b  Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia
,
Raju Suresh Kumar
b  Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia
,
a  Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan   Email: maruoka@kuchem.kyoto-u.ac.jp
c  School of Chemical Engineering and Light Industry, Guangdong University of Technology, No.100, West Waihuan Road, HEMC, Panyu District, Guangzhou, 510006, P. R. of China
› Author Affiliations
This work was partially supported by a Grant-in-Aid for Scientific Research from MEXT, Japan (Grant Number JP26220803, JP17H06450). The authors also extend their gratitude to the International Scientific Partnership Program (ISPP) at the King Saud University for financial support via ISPP#0072.
Further Information

Publication History

Received: 08 October 2018

Accepted after revision: 13 November 2018

Publication Date:
19 December 2018 (eFirst)

  

Published as part of the 30 Years SYNLETT – Pearl Anniversary Issue

Abstract

A new type of optically pure primary amino aromatic Tf-amide organocatalyst can be easily prepared from 8-amino-1-tetralone, and its chemical behavior was investigated in the context of asymmetric aldol and Mannich reactions. Most notably, the asymmetric aldol reaction proceeded smoothly in brine.

Supporting Information

 
  • References and Notes


    • Recent reviews on amine-based organocatalysts:
    • 1a Kano T, Maruoka K. Chem. Commun. 2008; 5465
    • 1b Lui X, Lin L, Feng X. Chem. Commun. 2009; 6145
    • 1c Yang H, Carter RG. Synlett 2010; 2827
    • 1d Giacalone F, Gruttadauria M, Agrigento P, Noto R. Chem. Soc. Rev. 2012; 41: 2406
    • 1e Melchiorre P. Angew. Chem. Int. Ed. 2012; 52: 9748
    • 1f Kano T, Maruoka K. Chem. Sci. 2013; 4: 907
    • 1g Duan J, Li P. Catal. Sci. Technol. 2014; 4: 311
    • 1h Kumar P, Sharma BM. Synlett 2018; 29: 1994
    • 1i Zhu L, Wang D, Jia Z, Lin Q, Huang M, Luo S. ACS Catal. 2018; 8: 5466

      Recent reviews on amino-catalyzed asymmetric aldol and Mannich reactions:
    • 2a Trost BM, Brindle CS. Chem. Soc. Rev. 2010; 39: 1600
    • 2b Hernández JG, Juaristi E. Chem. Commun. 2012; 48: 5396
    • 2c Heravi MM, Zadsirjan V, Dehghani M, Hosseintash N. Tetrahedron: Asymmetry 2017; 28: 587
    • 2d Saranya S, Harry NA, Krishnan KK, Anilkumar G. Asian J. Org. Chem. 2018; 7: 613
    • 2e Yamashita Y, Yasukawa T, Yoo W.-J, Kitanosono T, Kobayashi S. Chem. Soc. Rev. 2018; 47: 4388
    • 3a Kano T, Yamaguchi Y, Tokuda O, Maruoka K. J. Am. Chem. Soc. 2005; 127: 16408
    • 3b Kano T, Yamaguchi Y, Tanaka Y, Maruoka K. Angew. Chem. Int. Ed. 2007; 46: 1738
    • 3c Kano T, Yamamoto A, Maruoka K. Tetrahedron Lett. 2008; 49: 5369
    • 3d Kano T, Yamaguchi Y, Maruoka K. Angew. Chem. Int. Ed. 2009; 48: 1838
    • 3e Kano T, Yamaguchi Y, Maruoka K. Chem. Eur. J. 2009; 15: 6678

    • See also:
    • 3f Kano T, Ueda M, Takai J, Maruoka K. J. Am. Chem. Soc. 2006; 128: 6046
    • 4a Kano T, Sugimoto H, Maruoka K. J. Am. Chem. Soc. 2011; 133: 18130
    • 4b Kano T, Song S, Maruoka K. Angew. Chem. Int. Ed. 2012; 51: 1191
    • 4c Kano T, Song S, Maruoka K. Chem. Commun. 2012; 48: 7037
    • 5a Nakayama K, Maruoka K. J. Am. Chem. Soc. 2008; 130: 17666
    • 5b Moteki SA, Maruyama H, Nakayama K, Li H.-B, Petrova G, Maeda S, Morokuma K, Maruoka K. Chem. Asian. J. 2015; 10: 2112
    • 5c Lee H.-J, Moteki SA, Arumugam N, Almansour AI, Kumar RS, Liu Y, Maruoka K. Asian J. Org. Chem. 2017; 6: 1226
    • 5d Lee H.-J, Arumugam N, Almansour AI, Kumar RS, Maruoka K. Tetrahedron 2018; 74: 5263
  • 6 Moteki SA, Xu S, Arimitsu S, Maruoka K. J. Am. Chem. Soc. 2010; 132: 17074
  • 7 The synthesis of the primary amino aromatic Tf-amide organocatalysts 610 was carried out according to Scheme 2 (see Supporting Information for details).
  • 8 The absolute configurations of the catalysts were assigned based on the X-ray diffraction analysis of the sulfonamide intermediate of catalyst 9b. The corresponding data have been deposited at the Cambridge Crystallographic Data Center and can be obtained free of charge via www.ccdc.cam.ac.uk/getstructures. CCDC 1870339 contains the supplementary crystallographic data for this paper.

    • Reviews of amino-catalyzed asymmetric aldol reaction in aqueous media:
    • 9a Bhowmick S, Bhowmick KC. Tetrahedron: Asymmetry 2011; 22: 1945
    • 9b Kitanosono T, Kobayashi S. Adv. Synth. Catal. 2013; 355: 3095
    • 9c Mlynarski J, Bas S. Chem. Soc. Rev. 2014; 43: 557
    • 9d Bhowmick S, Mondal A, Ghosh A, Bhowmick KC. Tetrahedron: Asymmetry 2015; 26: 1215

      Selected examples for asymmetric aldol reaction in water or brine:
    • 10a Mase N, Nakai Y, Ohara N, Yoda H, Takabe K, Tanaka J, Barbas III CF. J. Am. Chem. Soc. 2006; 128: 734
    • 10b Ma X, Da C.-S, Yi L, Jia Y.-N, Guo Q.-P, Che L.-P, Wu F.-C, Wang J.-R, Li W.-P. Tetrahedron: Asymmetry 2009; 20: 1419
    • 10c Miura T, Kasuga H, Imai K, Ina M, Tada N, Imai N, Itoh A. Org. Biomol. Chem. 2012; 10: 2209
    • 10d Qiao Y, Chen Q, Lin S, Ni B, Headley AD. J. Org. Chem. 2013; 78: 2693
    • 10e Hu X.-M, Zhang D.-X, Zhang S.-Y, Wang P.-A. RSC Adv. 2015; 5: 39557
  • 11 General Procedure for the Asymmetric Aldol Reaction Using the Catalyst 9 for the Preparation of 11 To a mixture of catalyst 9 (3 mg, 5 mol%) and benzaldehyde (0.2 mmol) in brine (1.2 mL) was added ketone (6.0 mmol). The homogenous mixture was stirred at room temperature for the appropriate time until the reaction was completed (TLC). Then, a saturated NH4Cl solution was added, and the mixture was extracted with dichloromethane. The organic layer was dried over Na2SO4, filtered, and concentrated in vacuo. The residue was then purified by silica gel column chromatography (EtOAc/hexane = 1:3) to afford the product 11. (R)-2-[(S)-Hydroxy(4-nitrophenyl)methyl]cyclohexan-1-one (anti-11a) White solid. 1H NMR (CDCl3, 500 MHz): δ = 8.22–8.11 (m, 2 H), 7.52–7.49 (m, 2 H), 4.90 (d, J = 8.0 Hz, 1 H), 4.07, (br s, 1 H), 2.61–2.56 (m, 1 H), 2.52–2.47 (m, 1 H), 2.40–2.33, (m, 1 H), 2.14–2.08 (m, 1 H), 1.85–1.80 (m, 1 H), 1.72–1.62 (m, 1 H), 1.60–1.51 (m, 2 H), 1.42–1.33 (m, 1 H). 13C NMR (CDCl3, 125 MHz): δ = 214.7, 148.3, 147.5, 127.8, 123.5, 74.0, 57.1, 42.6, 30.7, 27.6, 24.6. HRMS (ESI): m/z calcd for C13H15O4NNa: 272.0893 [M + Na]+; found: 272.0895. [α]D 24 –11.2 (CHCl3, c 0.9, 99% ee).
  • 12 General Procedure for the Asymmetric Mannich Reaction Using Catalyst 9 for the Preparation of 13 To a mixture of catalyst 9 (3 mg, 5 mol%) and α-imino ester 12 (42 mg, 0.2 mmol) in THF (1.2 mL) was added ketone (6.0 mmol). The mixture was stirred at room temperature for 12 h. Then, a saturated NH4Cl solution was added, and the mixture was extracted with EtOAc. The organic layer was dried over Na2SO4, filtered, and concentrated in vacuo. The residue was then purified by silica gel column chromatography (EtOAc/hexane = 1:4) to afford the product 13. Ethyl (R)-2-[(4-Methoxyphenyl)amino]-2-[(S)-2-oxocyclohexyl]-acetate (anti-13a) Colorless oil. 1H NMR (CDCl3, 500 MHz): δ = 6.77–6.73 (m, 2 H), 6.64–6.61 (m, 2 H), 4.24 (br s, 1 H), 4.18–4.10 (m, 2 H), 3.98 (d, J = 4.5 Hz, 1 H), 3.73 (s, 3 H), 3.12–3.08 (m, 1 H), 2.45–2.40 (m, 1 H), 2.35–2.29 (m, 1 H), 2.13–2.09 (m, 1 H), 2.07–2.02 (m, 1 H), 1.96–1.87 (m, 2 H), 1.78–1.62 (m, 2 H), 1.21 (t, J = 7.5 Hz, 3 H). 13C NMR (CDCl3, 125 MHz): δ = 210.9, 173.0, 152.7, 142.1, 115.6, 114.7, 61.1, 59.0, 55.7, 53.5, 41.8, 30.5, 26.8, 24.5, 14.1. HRMS (ESI): m/z calcd for C17H23O4NNa: 328.1519 [M + Na]+; found: 328.1526. [α]D 24 –22.4 (CHCl3, c 0.7, 95% ee).