Rhodium(I)/Zn(OTf)2‐Catalyzed Asymmetric Ring Opening/Cyclopropanation of Oxabenzonorbornadienes with Phosphorus Ylides. Issue 44 (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 international edition. Volume 58:Issue 44(2019)
• Page Start: 15819
• Page End: 15823
• Publication Date: 2019-09-19
• Subjects: 1, 4-biselectrophiles -- asymmetric catalysis -- oxabenzonorbornadienes -- phosphorus ylides -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201909596
• Languages: English
• ISSNs: 1433-7851

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‐ylides : The use of Rh catalysis in the enantioselective ring‐opening/cyclopropanation reactions of various P‐ylides is demonstrated. This asymmetric reaction occurs through the cleavage of two bridgehead C−O bonds and the formation of two C−C bonds and constitutes the first highly enantioselective direct catalytic asymmetric cyclopropanation of stabilized P‐ylide nucleophiles.