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Synlett 2012; 23(13): 1990-1994
DOI: 10.1055/s-0032-1316582
letter
© Georg Thieme Verlag Stuttgart · New York

Design, Synthesis and Use of Novel 3,3′-Disubstituted 2,2′-Bipyridine-Based Chiral Ligands: Asymmetric Catalysis in Direct Aldol Reactions

Hong-Wu Zhao*
College of Life Science and Bioengineering, Beijing University of Technology, No.100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China, Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Hai-Long Li
College of Life Science and Bioengineering, Beijing University of Technology, No.100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China, Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Yuan-Yuan Yue
College of Life Science and Bioengineering, Beijing University of Technology, No.100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China, Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Xiao Qin
College of Life Science and Bioengineering, Beijing University of Technology, No.100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China, Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Zhi-Hui Sheng
College of Life Science and Bioengineering, Beijing University of Technology, No.100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China, Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Jin Cui
College of Life Science and Bioengineering, Beijing University of Technology, No.100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China, Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Shi Su
College of Life Science and Bioengineering, Beijing University of Technology, No.100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China, Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Xiu-Qing Song
College of Life Science and Bioengineering, Beijing University of Technology, No.100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China, Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Hong Yan
College of Life Science and Bioengineering, Beijing University of Technology, No.100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China, Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Ru-Gang Zhong
College of Life Science and Bioengineering, Beijing University of Technology, No.100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China, Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 12 May 2012

Accepted after revision: 29 May 2012

Publication Date:
23 July 2012 (online)

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Abstract

A wide range of chiral ligands based on the 2,2′-bipyridine scaffold were designed and synthesized. In complexation with metal Lewis acids, the reactivity and stereoselectivity of the prepared chiral ligands were examined in asymmetric catalytic direct aldol reactions, thus providing the desired products with high stereo­selectivities.

Key words

2,2′-bipyridine - bifunctional catalysis - direct aldol reaction - Lewis acid - Lewis base

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
  • Supporting Information
 

  • References and Notes

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  • 8 General Procedure of the Asymmetric Aldol Reaction Ketone (1 mL) and distilled H2O (25 μL) were added to a test tube with ligand 1 (1.9 mg, 0.005 mmol, 5 mol%) and stirred for 15 min, then Yb(OTf)3 (3.1 mg, 0.005 mmol, 5 mol%) was added to the mixture and stirred for 30 min. After the mixture was cooled to 0 °C, the corresponding aldehyde (0.1 mmol) was added, and the whole mixture was stirred at 0 °C for 96—168 h. After dried with anhyd Na2SO4 (200 mg), the reaction mixture was purified by flash chromatography on silica gel (eluent: EtOAc–PE) to give a mixture of syn- and anti-aldol products. The dr and ee values were determined by chiral HPLC analysis. 2-[Hydroxy(4-nitrophenyl)methyl]cyclohexanone (Table 2, Entry 1) Reaction time 96 h; yield 89% (a mixture of syn and anti products). anti-Diastereomer: 1H NMR (400 MHz, CDCl3): δ = 8.21 (d, J = 8.4 Hz, 2 H), 7.51 (d, J = 8.8 Hz, 2 H), 4.90 (dd, J = 2.8, 8.4 Hz, 1 H), 4.07 (d, J = 3.2 Hz, 1 H), 2.36–2.61 (m, 3 H), 2.09–2.14 (m, 1 H), 1.36–1.85 (m, 6 H). syn-Diastereomer: 1H NMR (400 MHz, CDCl3): δ = 8.21 (d, J = 8.4 Hz, 2 H), 7.49 (d, J = 8.8 Hz, 2 H), 5.49 (s, 1 H), 3.17 (d, J = 2.8 Hz, 1 H), 2.36–2.65 (m, 3 H), 2.10–2.13 (m, 1 H), 1.51–1.88 (m, 6 H). HPLC separation conditions: Chiralcel AD, solvent: hexane–i-PrOH (90:10), flow rate: 1.0 mL/min, λ = 254 nm; retention time: t R (syn) = 17.655 min; t R (syn) = 20.648 min; t R (anti) = 23.230 min; t R (anti) = 31.517 min; dr (anti/syn) = 95:5; ee (anti) = 85%.