Direct catalytic asymmetric Mannich-type reaction of unmodified ketones utilizing the cooperation of an AlLibis(binaphthoxide) complex and La(OTf)3·nH2O

Synthesis and structure of an air-stable organoantimony complex and its use as a catalyst for direct diastereoselective Mannich reactions in water

“…Impressive accomplishments have been made in diasteroselective synthesis over various Lewis acid catalysts [3]. Shibasaki and co-workers reported for the first time the direct Mannich-type reaction of unmodified ketones catalyzed by lanthanum complex [5]. Kobayashi et al reported that FeCl 2 together with a (R)-3.3 0 -I 2 BINOL complex is effective for the Mannich reaction of imines with silyl enolates [6].…”

“…Most of the applications are focused on in vitro antitumour activity and organic reactivity [21][22][23][24]. Kakusawa et al reported that hypervalent organoantimony compounds with a tetrahydrodibenzo[c,f] [1,5]azastibocine framework are agents highly efficient for cross-coupling reactions [27]. Recently, organoantimony oxide was synthesized and found to be recoverable reagent efficient for CO 2 chemical fixation [28].…”

The Proline‐Catalyzed Mannich Reaction and the Advent of Enamine Catalysis

“…It can be considered a breakthrough when Shibasaki and co-workers [10]. designed a direct catalytic enantioselective three-component Mannich reaction of propiophenone (4), paraformaldehyde, and pyrrolidine that gave the corresponding product 5 with encouraging enantioselectivity (82 : 18 er) but still in relatively low yield (16%) (Scheme 10.3).…”

Asymmetrische katalytische Aminoalkylierungen: neue leistungsstarke Methoden zur enantioselektiven Synthese von Aminosäurederivaten, Mannich-Basen und Homoallylaminen

“…Hierdurch gelang es nicht nur, HCN oder dessen Syntheseäquivalente, [6] sondern auch zahlreiche andere Nucleophile asymmetrisch zu aminoalkylieren (z. B. Trimethylsilylenolether, die sich von Estern [7, 8, 9a] oder Ketonen [9] ableiten, Alkene, [10] Allyltributylstannan, [11a] Allyltrimethylsilane [9a, 11b] und Ketone [12] ). Auf diese Weise wurden effiziente Wege zur enantioselektiven Herstellung einer Vielzahl wertvoller Synthesebausteine geschaffen (z.…”

“…[6] a-und b-Aminosäurederivate, [7±10] Homoallylamine [9a, 10, 11] sowie b-Aminoketone [9,12] ). Bei der Mehrzahl der bisher publizierten Methoden werden Iminoverbindungen verwendet, die als zweizähnige Liganden fungieren und mit den chiralen Lewis-Säure-Katalysatoren Chelatkomplexe bilden können.…”