We found a match
Your institution may have rights to this item. Sign in to continue.
- Title
Catalytic Regio‐ and Enantioselective Protonation for the Synthesis of Chiral Allenes: Synergistic Effect of the Counterion and Water.
- Authors
Lin, Qianchi; Zheng, Sujuan; Chen, Long; Wu, Jin; Li, Jinzhao; Liu, Peizhi; Dong, Shunxi; Liu, Xiaohua; Peng, Qian; Feng, Xiaoming
- Abstract
A highly enantioselective tandem Pudovik addition/[1,2]‐phospha‐Brook rearrangement of α‐alkynylketoamides with diarylphosphine oxides was achieved with a N,N′‐dioxide/ScIII complex as the catalyst. This protocol features broad substrate scope, high regio‐ and enantioselectivity, and good functional‐group compatibility, providing a straightforward route to various trisubstituted allenes with a diarylphosphinate functionality in good yields with high enantioselectivities (up to 97 % yield, 96 % ee). Control experiments and theoretical calculations revealed that a synergistic effect of the counterion and water was critical for the regio‐ and enantioselective protonation after [1,2]‐phospha‐Brook rearrangement. The synthetic utility of this methodology was demonstrated by the conversion of products into complex bridged polycyclic architectures through intramolecular dearomatizing arene/allene cycloaddition.
- Subjects
ALLENE; PROTON transfer reactions; LEWIS acids
- Publication
Angewandte Chemie, 2022, Vol 134, Issue 27, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202203650