Michael Addition Catalyzed by Chiral Secondary Amine Phosphoramide Using Fluorinated Silyl Enol Ethers: Formation of Quaternary Carbon Stereocenters

• Published in: Angewandte Chemie International Edition Vol. 54; no. 25; pp. 7381 - 7385
• Main Authors: Yu, Jin-Sheng, Liao, Fu-Min, Gao, Wei-Ming, Liao, Kui, Zuo, Run-Lin, Zhou, Jian
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 15.06.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Amines; asymmetric catalysis; Bearing; Carbon; Catalysts; Chemistry; Chemistry, Multidisciplinary; chirality; Ethers; Fluorination; fluorine; Formations; Michael reaction; Olefins; organocatalysis; Physical Sciences; Science & Technology; ALDOL; DIFLUOROENOXYSILANES; chirality; amines; LEWIS-BASE ACTIVATION; 3,3'-DISUBSTITUTED OXINDOLES; asymmetric catalysis; ORGANOCATALYTIC ASYMMETRIC-SYNTHESIS; organocatalysis; 3+2 ANNULATION; HIGHLY ENANTIOSELECTIVE CONSTRUCTION; TRIMETHYLSILYL CYANIDE; STRECKER REACTION; fluorine; CONJUGATE ADDITION
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201501747

A chiral secondary amine phosphoramide was developed and identified as a powerful catalyst for the Mukaiyama–Michael addition of fluorinated enol silyl ethers to tetrasubstituted olefins. The resulting products are obtained with high enantioselectivities and contain a quaternary carbon stereocenter bearing either a difluoroalkyl or monofluoroalkyl group. Four C′s: The chiral secondary amine phosphoramide A was developed and serves as a powerful catalyst for the Michael addition of fluorinated enol silyl ethers to tetrasubstituted olefins. The resulting products are obtained with high enantioselectivities and contain a quaternary carbon stereocenter bearing either a difluoroalkyl or monofluoroalkyl group. TMS=trimethylsilyl.