Asymmetric Synthesis of β‐Amino Nitriles through a Sc^III‐Catalyzed Three‐Component Mannich Reaction of Silyl Ketene Imines

Abstract

Scheme 2. Transformations of the product 6 a into other derivatives. Reaction conditions: a) 1) AlCl 3 , LiAlH 4 , Et 2 O; 2) Et 3 N, Boc 2 O; b) Pd-(OAc) 2 , PPh 3 , CH 3 CH = NOH, EtOH/H 2 O (4:1), reflux; c) 1) K 2 CO 3 , MeI, acetone, 93%; 2) CAN, CH 3 CN/H 2 O, then Et 3 N, Boc 2 O. Ar = 2-OH-4-MeC 6 H 3 . Boc = tert-butyloxycarbonyl. Scheme 3. Proposed catalytic model. Angewandte Chemie 3475

Cyanoalkylierung: Alkylnitrile in katalytischen C‐C‐Kupplungen

“…[59] Von tert-Butyl-geschützten Cyanhydrinen abgeleitete N-Silyloxyketenimine (Schema 33 b) gehen unter ähnlichen Reaktionsbedingungen ebenfalls Lewis-Basen-katalysierte Aldoladditionen ein. [62] Die . [61] Feng und Mitarbeiter verwendeten SKIs als Nucleophile in einer Sc-katalysierten Mannich-Dreikomponentenreaktion unter Verwendung des Liganden 38 zur Synthese enantiomerenangereicherter b-Aminonitrile (Schema 35).…”

“…[61] Feng und Mitarbeiter verwendeten SKIs als Nucleophile in einer Sc-katalysierten Mannich-Dreikomponentenreaktion unter Verwendung des Liganden 38 zur Synthese enantiomerenangereicherter b-Aminonitrile (Schema 35). [62] Die . .…”

Crystal structure of 2,4-dinitrophenyl 4-methylbenzenesulfonate: a new polymorph

“…FEMROF: Ichikawa et al, 2004), ethoxy (e.g. HIRHOG: Ramachandran et al, 2007), chlorine (OJENEW: Vembu et al, 2003b) and alkyl amine (PERFEZ: Zhao et al, 2013). The CSD contains three additional structures where the position ortho to the sulfonic ester bears a nitro group.…”

Template catalysis by manganese pincer complexes: oxa- and aza-Michael additions to unsaturated nitriles

“…Compared with the oxa-Michael addition, much lower activity was observed for the aza-Michael addition reactions of amines to unsaturated nitriles even at higher temperatures. Since bamino nitriles are both pharmacologically and synthetically of great importance, 16,17 it is desirable to discover metal catalysts with high activity under mild conditions for the aza-Michael addition reactions of unsaturated nitriles with amines.…”