Comprehensive Report
One Stone Two Birds—Enantioselective Bimetallic Catalysis for α-Amino Acid Derivatives with an Allene Unit
Junzhe Xiao,
Haibo Xu,
Xiaohong Huo,
Wanbin Zhang,
Shengming Ma,
Junzhe Xiao
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
University of Chinese Academy of Sciences, Beijing, 100049 China
Search for more papers by this authorHaibo Xu
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
University of Chinese Academy of Sciences, Beijing, 100049 China
Search for more papers by this authorXiaohong Huo
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering and School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorWanbin Zhang
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering and School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorCorresponding Author
Shengming Ma
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
Research Centre for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Lu, Shanghai, 200433 China
E-mail: [email protected]Search for more papers by this authorJunzhe Xiao,
Haibo Xu,
Xiaohong Huo,
Wanbin Zhang,
Shengming Ma,
Junzhe Xiao
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
University of Chinese Academy of Sciences, Beijing, 100049 China
Search for more papers by this authorHaibo Xu
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
University of Chinese Academy of Sciences, Beijing, 100049 China
Search for more papers by this authorXiaohong Huo
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering and School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorWanbin Zhang
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering and School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240 China
Search for more papers by this authorCorresponding Author
Shengming Ma
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032 China
Research Centre for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Lu, Shanghai, 200433 China
E-mail: [email protected]Search for more papers by this authorMain observation and conclusion
A highly enantioselective 2,3-allenylation of acyclic and cyclic α-imino carboxylates via a synergistic bimetallic Pd/Cu catalysis with the same commercially available (R,Rp)-iPr-FOXAP (also as Phosferrox, (R,R)-[2-(4’-i-propyloxazolin-2’-yl)ferrocenyl]diphenyl phosphine) ligand for both metals affording optically active 2,3-butadienyl α-amino acid derivatives in high to excellent yields with excellent enantioselectivities has been developed. The synthetic versatility of this reaction has been demonstrated by gram-scale synthesis, a catalytic enantioselective synthesis of naturally occurring (S)-2-amino-4,5-hexadienoic acid A, and conversions to several useful chemicals, such as optically active α-amino acids, β-amino alcohols, potential chiral oxazoline ligands bearing an allenic moiety, and bicyclic ketone compounds. A mechanism involving the roles of two metals and the single chiral ligand has been extensively studied based on the isolation of key palladium pre-catalyst and control experiments.
Supporting Information
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Appendix S1: Supporting Information |
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