Axial Ligand Enables Synthesis of Allenylsilane through Dirhodium(II) Catalysis
Wendeng Li
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
Search for more papers by this authorRui Wu
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
Search for more papers by this authorHao Ruan
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
Search for more papers by this authorBo Xiao
Key Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, 518055 P. R. China
Search for more papers by this authorXiang Gao
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
Search for more papers by this authorProf. Dr. Huanfeng Jiang
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
Search for more papers by this authorDr. Kai Chen
College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083 P. R. China
Search for more papers by this authorCorresponding Author
Dr. Tian-Yu Sun
Key Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, 518055 P. R. China
Institute of Molecular Chemical Biology, Shenzhen Bay Laboratory, Shenzhen, 518132 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Shifa Zhu
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou, 310018 P. R. China
Search for more papers by this authorWendeng Li
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
Search for more papers by this authorRui Wu
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
Search for more papers by this authorHao Ruan
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
Search for more papers by this authorBo Xiao
Key Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, 518055 P. R. China
Search for more papers by this authorXiang Gao
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
Search for more papers by this authorProf. Dr. Huanfeng Jiang
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
Search for more papers by this authorDr. Kai Chen
College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083 P. R. China
Search for more papers by this authorCorresponding Author
Dr. Tian-Yu Sun
Key Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, 518055 P. R. China
Institute of Molecular Chemical Biology, Shenzhen Bay Laboratory, Shenzhen, 518132 P. R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Shifa Zhu
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640 P. R. China
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou, 310018 P. R. China
Search for more papers by this authorAbstract
Described herein is a dirhodium(II)-catalyzed silylation of propargyl esters with hydrosilanes, using tertiary amines as axial ligands. By adopting this strategy, a range of versatile and useful allenylsilanes can be achieved with good yields. This reaction not only represents a SN2′-type silylation of the propargyl derivatives bearing a terminal alkyne moiety to synthesize allenylsilanes from simple hydrosilanes, but also represents a new application of dirhodium(II) complexes in catalytic transformation of carbon-carbon triple bond. The highly functionalized allenylsilanes that are produced can be transformed into a series of synthetically useful organic molecules. In this reaction, an intriguing ON-OFF effect of the amine ligand was observed. The reaction almost did not occur (OFF) without addition of Lewis base amine ligand. However, the reaction took place smoothly (ON) after addition of only catalytic amount of amine ligand. Detailed mechanistic studies and density functional theory (DFT) calculations indicate that the reactivity can be delicately improved by the use of tertiary amine. The fine-tuning effect of the tertiary amine is crucial in the formation of the Rh−Si species via a concerted metalation deprotonation (CMD) mechanism and facilitating β-oxygen elimination.
Conflict of Interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
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