Застосування хіральних сульфінільних ауксиларів в асиметричному синтезі фторованих амінів і амінокислот

• Datum: 2023
• Hauptverfasser: Lyutenko, Nataliya V., Sorochinsky, Alexander E., Soloshonok, Vadim A.
• Format: Artikel
• Sprache: English
• Veröffentlicht: V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2023
• Schlagworte: aсиметричний синтез; сульфоксиди; α-фторалкіламінопохідні; α- і β-амінокислоти
• Online Zugang: https://bioorganica.com.ua/index.php/journal/article/view/50
• Назва журналу: Ukrainica Bioorganica Acta

This review article covers the developments made in collaboration by groups of Professors V. P. Kukhar and P. Bravo to the synthetic applications of sulfinyl compounds as versatile chiral auxiliaries for asymmetric preparation of fluorinated amines and amino acids. The potential of the sulfinyl chiral auxiliaries in the field of stereoselective transformations of fluorinated substrates is demonstrated by diastereoselective methylene transfer from diazomethane to the carbonyl of β-keto-γ-fluoroalkyl sulfoxides as a general approach for preparation of various fluorinated oxirane derivatives, diastereoselective sulfoxide anions addition to fluorinated imines leading to convenient preparation of α-fluoroalkyl α-amino acids, hydroxy amines, and amines, diastereoselective Mannich-type reaction between N-tert-butanesulfinyl-3,3,3-trifluoroacetaldimine and protected alkyl glycolates furnishing β-trifluoromethyl isoserine derivatives and diastereoselective additions of phosphite or α-phosphonate anions to N-tert-butanesulfinyl-3,3,3-trifluoroacetaldimine using for synthesis of trifluoromethylated α- and β-aminophosphonic acids. Furthermore, diastereoselective additions of Reformatsky reagent derived from bromodifluoroethyl acetate as well as α,α-difluorophosphonate anions to N-p-toluenesulfinyl imines allowing convenient preparation of a,a-difluoro-b-amino acids and α,α-difluoro-β-amino phosphonates in enantiomerically pure form are described. Effect of fluorine on the mechanism and stereochemical outcome of these reactions is briefly discussed.