Synthesis of <italic>C</italic><sub>1</sub>-symmetric primary-secondary diamines and their application in the enantioselective Henry reaction

doi:10.1007/s11705-013-1343-4

Front Chem Sci Eng

2013, Vol. 7

Issue (4) : 408-414 https://doi.org/10.1007/s11705-013-1343-4

RESEARCH ARTICLE

Synthesis of C₁-symmetric primary-secondary diamines and their application in the enantioselective Henry reaction

Lili ZHANG¹, Ming LIU¹, Shijun MA², Yaodong HUANG¹(

), Yongmei WANG²(

)

1. Key Laboratory of Systems Bioengineering, Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China; 2. State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Nankai University, Tianjin 300071, China

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Abstract

Two new C₁-symmetric primary-secondary diamines were synthesized via the reaction of (S,S)-1,2-diphenyl ethylene diamine with 3,5-ditert-butyl salicylaldehyde and salicylaldehyde, respectively, followed by reduction with NaBH₄. The combination of the ligand from 3,5-ditert-butyl salicylaldehyde with CuBr could effciently catalyze the Henry reaction to afford β-nitroalkanols in moderate to good yields (up to 87%) and high enantioselectivities (up to 88% ee). A possible mechanism of the reaction was proposed.

Keywords enantioselective Henry reaction C₁-symmetric diamines asymmetric reaction nitroalkanol

Corresponding Author(s): HUANG Yaodong,Email:huangyaodong@tju.edu.cn; WANG Yongmei,Email:ymw@nankai.edu.cn

Issue Date: 05 December 2013

Cite this article:

Lili ZHANG,Ming LIU,Shijun MA, et al. Synthesis of C₁-symmetric primary-secondary diamines and their application in the enantioselective Henry reaction[J]. Front Chem Sci Eng, 2013, 7(4): 408-414.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-013-1343-4
https://academic.hep.com.cn/fcse/EN/Y2013/V7/I4/408

Fig.1 Synthetic route to chiral -symmetric primary-secondary diamine ligands

Tab.1 Screening of the ligands and copper salts in the asymmetric Henry reaction

Fig.2

Tab.2 Screening the solvents in the asymmetric Henry reaction

Fig.3

Tab.3 Effects of bases on the Cu(I)/ complex catalyzed enantioselective Henry reaction

Fig.4

Tab.4 Enantioselective Henry reaction of aldehydes with nitroalkanes catalyzed by

Fig.5

Fig.6 Proposed transition state for the catalytic asymmetric Henry reaction

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