Rhodium(I)/Zn(OTf)2‐Catalyzed Asymmetric Ring Opening/Cyclopropanation of Oxabenzonorbornadienes with Phosphorus Ylides. (19th September 2019)

• Record Type: Journal Article
• Authors: Chen, Tao; Gan, Lifei; Wang, Ran; Deng, Yuhua; Peng, Fangzhi; Lautens, Mark; Shao, Zhihui
• Is Part Of: Angewandte Chemie. Volume 131:Number 44(2019)
• Page Start: 15966
• Page End: 15970
• Publication Date: 2019-09-19
• Subjects: 1, 4-Bis-Elektrophile -- Asymmetrische Katalyse -- Oxabenzonorbornadiene -- Phosphorylide -- Rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201909596
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The strong binding ability of P‐ylides with transition metals limits the utilization of stabilized P‐ylide as nucleophiles in asymmetric organometallic catalysis. Herein we describe the first rhodium‐catalyzed asymmetric ring‐opening reaction of P‐ylides utilizing oxabicyclic alkenes as the electrophilic partner. Various P‐ylides including ester‐, ketone‐ and amide‐style P‐ylides are all applicable. This asymmetric reaction occurs through the cleavage of two bridgehead C−O bonds and the formation of two C−C bonds, and oxabenzonorbornadienes are used as 1, 4‐biselectrophiles, thus providing access to benzonorcaradienes in good yields with high enantioselectivity and perfect diastereoselectivity. The present protocol also constitutes the first highly enantioselective direct catalytic asymmetric cyclopropanation of stabilized P‐ylide nucleophiles. Abstract : P‐Ylide : Die Anwendung einer Rh‐Katalyse in der enantioselektiven Ringöffnung/Cyclopropanierung diverser P‐Ylide wird demonstriert. Diese asymmetrische Reaktion beinhaltet die Spaltung zweier Brückenkopf‐C‐O‐Bindungen und die Bildung zweier C‐C‐Bindungen und stellt die erste hoch enantioselektive direkte katalytische asymmetrische Cyclopropanierung von stabilisierten P‐Ylid‐Nukleophilen dar.