Ruthenium-Catalyzed α-Regioselective Hydroboration of Allenes
Dr. Yun-Xuan Tan
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Y.-X. T. and S. L. contributed equally to this work.
Search for more papers by this authorDr. Shijia Li
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Shenzhen Bay Laboratory, Shenzhen, 518055 China
Y.-X. T. and S. L. contributed equally to this work.
Search for more papers by this authorDr. Liang Chen
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Search for more papers by this authorJing Huang
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Shenzhen Bay Laboratory, Shenzhen, 518055 China
Search for more papers by this authorDr. Chaoshen Zhang
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Search for more papers by this authorCorresponding Author
Prof. Dr. Lijuan Song
School of Science, Harbin Institute of Technology (Shenzhen), Shenzhen
Search for more papers by this authorProf. Dr. Xinhao Zhang
Shenzhen Bay Laboratory, Shenzhen, 518055 China
Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen, 518055 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Yun-Dong Wu
Shenzhen Bay Laboratory, Shenzhen, 518055 China
Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen, 518055 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Jianwei Sun
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Search for more papers by this authorDr. Yun-Xuan Tan
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Y.-X. T. and S. L. contributed equally to this work.
Search for more papers by this authorDr. Shijia Li
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Shenzhen Bay Laboratory, Shenzhen, 518055 China
Y.-X. T. and S. L. contributed equally to this work.
Search for more papers by this authorDr. Liang Chen
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Search for more papers by this authorJing Huang
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Shenzhen Bay Laboratory, Shenzhen, 518055 China
Search for more papers by this authorDr. Chaoshen Zhang
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Search for more papers by this authorCorresponding Author
Prof. Dr. Lijuan Song
School of Science, Harbin Institute of Technology (Shenzhen), Shenzhen
Search for more papers by this authorProf. Dr. Xinhao Zhang
Shenzhen Bay Laboratory, Shenzhen, 518055 China
Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen, 518055 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Yun-Dong Wu
Shenzhen Bay Laboratory, Shenzhen, 518055 China
Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen, 518055 China
Search for more papers by this authorCorresponding Author
Prof. Dr. Jianwei Sun
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, 999077, Hong Kong SAR China
Search for more papers by this authorAbstract
Hydroboration of allenes is powerful and atom-economic approach to the synthesis of organoboranes, such as the highly versatile allylboranes. However, regarding regiocontrol, existing methods uniformly deliver the boron functionality to the less hindered β- or γ-position, but not the α-position. The latter is particularly challenging for allenes with substantial steric difference between the two terminals and lacking electronic bias (e.g., 1,1-disubstituted allenes). Herein we report the first highly efficient ruthenium-catalyzed hydroboration of allenes featuring exclusive α-regioselectivity, providing access to sterically hindered allyl boranes that are limitedly accessible by conventional methods. DFT studies suggested that the unusual α-regioselectivity is attributed to the disfavored reductive elimination at the γ-position due to the high energy cost required to overcome the agostic interaction and rotation of the key π-allyl intermediates. This protocol is also applicable to the previously unprecedented α-hydroalkynylation and underdeveloped α-hydrosilylation of allenes, thus complementing known catalytic systems and providing convenient access to highly congested yet densely-functionalized allyl silanes and skipped enynes bearing a fully-substituted allylic carbon center. It is expected that this ruthenium-catalyzed system can serve as a new platform for the development of other hydrofunctionalization processes with unorthodox selectivity.
Conflict of Interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
Supporting Information
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