Highly Enantioselective Michael Addition of Acetone to Nitro Olefins Catalyzed by Chiral Bifunctional Primary Amine-Thiophosphoramide Catalyst

• Published in: European Journal of Organic Chemistry Vol. 2010; no. 30; pp. 5777 - 5781
• Main Authors: Lu, Aidang, Liu, Tao, Wu, Ronghua, Wang, Youming, Zhou, Zhenghong, Wu, Guiping, Fang, Jianxin, Tang, Chuchi
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.10.2010; WILEY‐VCH Verlag; Wiley; Wiley-VCH
• Subjects: Alicyclic compounds; Alicyclic compounds, terpenoids, prostaglandins, steroids; Catalysis; Catalysts: preparations and properties; Chemistry; Chemistry, Organic; Chiral thiophos­phoramide; Enantioselectivity; Exact sciences and technology; General and physical chemistry; Kinetics and mechanisms; Michael addition; Nitro olefins; Noncondensed benzenic compounds; Organic chemistry; Physical Sciences; Preparations and properties; Reactivity and mechanisms; Science & Technology; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Michael addition; ACID; Enantioselectivity; THIOUREA; Nitro olefins; Chiral thiophosphoramide; ALDOL REACTIONS; ALDEHYDES; KETONES; NITROSTYRENES; ASYMMETRIC ORGANOCATALYSTS; NITROOLEFINS; CONJUGATE ADDITION; WATER; Nitro compound; Catalytic reaction; Cyclohexane derivatives; Bifunctional compound; Chiral compound; Protic solvent; Phosphorus Organic compounds; Olefin; Asymmetric synthesis; Phenols; Enantiomeric excess; Aromatic compound; Chemical synthesis; Primary amine; Catalyst; Ethylenic compound; Organic thioamidophosphate; Acetone
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201000945

A series of bifunctional primary amine‐thiophosphoramides were synthesized, which proven to be effective organocatalysts for the asymmetric Michael reaction of acetone to both aryl and alkyl nitro olefins in the presence of phenol as a protic additive. The corresponding adducts were obtained in excellent chemical yields (up to >99 %) with excellent enantioselectivities (up to 97 % ee). A novel chiral phosphoramide functions well as an efficient bifunctional organocatalyst for the asymmetric Michael addition of acetone, one of the most challenge substrate in Michael addition, to nitro olefinsto afford the corresponding syntheticvaluable γ‐nitro ketones in good to excellent yield with high levels of enantioselectivities (up to 97 % ee, respectively).