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

Hyo-Jun Lee; Natarajan Arumugam; Abdulrahman I. Almansour; Raju Suresh Kumar; Keiji Maruoka

doi:10.1055/s-0037-1610408

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

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

Authors

Hyo-Jun Lee

^aDepartment of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan eMail: maruoka@kuchem.kyoto-u.ac.jp
Natarajan Arumugam

^bDepartment of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia
Abdulrahman I. Almansour

^bDepartment of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia
Raju Suresh Kumar

^bDepartment of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia
Keiji Maruoka *

^aDepartment of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan eMail: maruoka@kuchem.kyoto-u.ac.jp

^cSchool of Chemical Engineering and Light Industry, Guangdong University of Technology, No.100, West Waihuan Road, HEMC, Panyu District, Guangzhou, 510006, P. R. of China

Abstract

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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.

Key words

asymmetric synthesis - aldol reaction - organocatalyst - brine - Mannich reaction

Volltext

Referenzen

References and Notes

Recent reviews on amine-based organocatalysts:

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Recent reviews on amino-catalyzed asymmetric aldol and Mannich reactions:

2a Trost BM, Brindle CS. Chem. Soc. Rev. 2010; 39: 1600
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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
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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 6–10 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.

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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

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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).

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