Enantioselective Synthesis of Multisubstituted Allenes by Cooperative Cu/Pd‐Catalyzed 1, 4‐Arylboration of 1, 3‐Enynes. (28th November 2019)

• Record Type: Journal Article
• Authors: Liao, Yang; Yin, Xuemei; Wang, Xihong; Yu, Wangzhi; Fang, Dongmei; Hu, Lianrui; Wang, Min; Liao, Jian
• Is Part Of: Angewandte Chemie. Volume 132:Number 3(2020)
• Page Start: 1192
• Page End: 1196
• Publication Date: 2019-11-28
• Subjects: Allene -- Kupfer -- Palladium -- Enantioselektivität -- Synthesemethoden; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201912703
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A cooperative Cu/Pd‐catalyzed enantioselective synthesis of multisubstituted allenes is established. By employing chiral sulfoxide phosphine (SOP)/Cu and PdCl2 (dppf) complexes as catalysts, the 1, 4‐arylboration of 1, 3‐enynes provides an efficient approach to trisubstituted chiral allenes with up to 92 % yield and 97:3 er. Furthermore, by using 2‐substituted 1, 3‐enynes as substrates, the tetrasubstituted chiral allenes were successfully generated using this strategy. Finally, theoretical calculations indicate that the transmetallation of the allenylcopper species is the rate‐limiting step of this transformation. Abstract : Eine kooperative Cu/Pd‐katalysierte enantioselektive 1, 4‐Arylborierung von 1, 3‐Eninen ergibt exzellente Ausbeuten und Enantioselektivitäten mit einem breiten Substratspektrum. Tri‐ und tetrasubstituierte axial‐chirale Allene wurden hergestellt. Theoretische Studien zeigen, dass die Transmetallierung der Allenylkupfer‐Spezies der geschwindigkeitsbestimmende Schritt ist.