Chiral Lewis Base‐Catalyzed, Enantioselective Reduction of Unprotected β‐Enamino Esters with Trichlorosilane. Issue 7 (23rd February 2016)

• Record Type: Journal Article
• Authors: Ye, Jianheng; Wang, Chao; Chen, Lin; Wu, Xinjun; Zhou, Li; Sun, Jian
• Is Part Of: Advanced synthesis & catalysis. Volume 358:Issue 7(2016)
• Page Start: 1042
• Page End: 1047
• Publication Date: 2016-02-23
• Subjects: β‐amino esters -- asymmetric hydrosilylation -- Lewis bases -- reduction -- trichlorosilane; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201501061
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: Catalytic asymmetric reduction of N‐unsubstituted β‐enamino esters represents a major challenge for asymmetric catalysis. In this paper, the first organocatalytic system that could be used for the asymmetric hydrosilylation of N‐unsubstituted β‐enamino esters has been developed. Using N ‐ tert ‐butylsulfinyl‐L ‐proline‐derived amides andL ‐pipecolinic acid‐derived formamides as catalyst, a broad range of β‐aryl‐ and β‐alkyl‐substituted free β‐amino esters could be prepared with high yields and enantioselectivities. The practicality was illustrated by the gram‐scale asymmetric synthesis of ethyl ( R )‐3‐amino‐3‐phenylpropanoate and isopropyl ( S )‐3‐amino‐4‐(2, 3, 5‐trifluorophenyl)butanoate. The resulting product can be smoothly transformed to the FDA approved medicines dapoxetine and sitagliptin in a short synthetic route. Abstract :