Synlett 2014; 25(2): 293-297
DOI: 10.1055/s-0033-1340289
letter
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Direct Michael Reactions of Cyclohexanone with Aromatic Nitroolefins in Water Catalyzed by Novel Axially Unfixed Biaryl-Based Bifunctional Organocatalysts

Hong-Wu Zhao*
College of Life Science and Bio-engineering, Beijing University of Technology, 100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China   Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Zhao Yang
College of Life Science and Bio-engineering, Beijing University of Technology, 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 Bio-engineering, Beijing University of Technology, 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 Bio-engineering, Beijing University of Technology, 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 Bio-engineering, Beijing University of Technology, 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 Bio-engineering, Beijing University of Technology, 100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China   Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Wei Meng
College of Life Science and Bio-engineering, Beijing University of Technology, 100 Pingleyuan, Chaoyang District, Beijing 100124, P. R. of China   Fax: +86(10)67396200   Email: hwzhao@bjut.edu.cn
,
Xiao-Yu Guo
College of Life Science and Bio-engineering, Beijing University of Technology, 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: 11 September 2013

Accepted after revision: 17 October 2013

Publication Date:
04 December 2013 (online)


Abstract

A new family of axially unfixed biaryl-based water-compatible bifuctional organocatalysts were designed and synthesized for the asymmetric direct Michael reaction of cyclohexanone with various nitroolefins in water. One of the organocatalysts incorporates pyrrolidine and arylsulfonamide motifs as active organocatalytic sites, and axially unfixed biaryl as a skeleton; with this organocatalyst, the direct Michael reactions proceeded readily, furnishing the desired Michael adducts in high yields (up to 99% yield) with high levels of stereocontrol (up to >99:1 dr and 94% ee).

Supporting Information

 
  • References and Notes


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  • 9 Asymmetric Michael Addition; General Procedure: A suspension of catalyst 2a (4.2 mg, 0.01 mmol), PhCO2H (1.2 mg, 0.01 mmol) and cyclohexanone (104 μL, 1.0 mmol) in water (0.5 mL) was stirred at r.t. for 30 min. Nitroolefin (0.1 mmol) was added and the mixture was stirred for the time indicated in the tables. The mixture was extracted with CH2Cl2 (2 × 5 mL) and the organic layers were dried over anhydrous Na2SO4 and concentrated in vacuo. A mixture of syn- and anti-Michael products was obtained through flash chromatography on silica gel (petroleum–EtOAc, 5:1). The dr and ee values were determined by chiral HPLC analysis [Chiralcel AS-H; hexane–2-propanol, 85:15; 1.0 mL/min; λ = 210 nm; tR = 13.91 (minor), 23.41 (major) min]. (S)-2-[(R)-2-Nitro-1-phenylethyl]cyclohexanone (Table 2, entry 1): Reaction time: 12 h. Yield: 85%; dr = 97:3 (syn/anti); ee = 89% (syn).1H NMR (400 MHz, CDCl3): δ = 7.28–7.32 (m, 3 H), 7.16–7.17 (m, 2 H), 4.94 (dd, J = 12.4, 4.0 Hz, 1 H), 4.60–4.66 (m, 1 H), 3.76 (d, J = 4.0 Hz, 1 H), 2.69 (s, 1 H), 2.38–2.49 (m, 2 H), 2.07 (d, J = 3.2 Hz, 1 H), 1.55–1.80 (m, 4 H), 1.19–1.28 (m, 1 H).