Asymmetric Catalytic Formal 1,4-Allylation of β,γ-Unsaturated α-Ketoesters: Allylboration/Oxy-Cope Rearrangement
Qiong Tang
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorDr. Kai Fu
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorPeiran Ruan
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Shunxi Dong
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorProf. Dr. Zhishan Su
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorProf. Dr. Xiaohua Liu
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Xiaoming Feng
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorQiong Tang
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorDr. Kai Fu
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorPeiran Ruan
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Shunxi Dong
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorProf. Dr. Zhishan Su
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorProf. Dr. Xiaohua Liu
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Xiaoming Feng
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064 China
Search for more papers by this authorAbstract
A highly enantioselective formal conjugate allyl addition of allylboronic acids to β,γ-unsaturated α-ketoesters has been realized by employing a chiral NiII/N,N′-dioxide complex as the catalyst. This transformation proceeds by an allylboration/oxy-Cope rearrangement sequence, providing a facile and rapid route to γ-allyl-α-ketoesters with moderate to good yields (65–92 %) and excellent ee values (90–99 % ee). The isolation of 1,2-allylboration products provided insight into the mechanism of the subsequent oxy-Cope rearrangement reaction: substrate-induced chiral transfer and a chiral Lewis acid accelerated process. Based on the experimental investigations and DFT calculations, a rare boatlike transition-state model is proposed as the origin of high chirality transfer during the oxy-Cope rearrangement.
Conflict of interest
The authors declare no conflict of interest.
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