Transient-axial-chirality controlled asymmetric rhodium-carbene C(sp2)-H functionalization for the synthesis of chiral fluorenes
| Autor: | Ju Cai, Xinfang Xu, Zhi-Xiang Yu, Sailan Chang, Chao Pei, Yang Zheng, Kuiyong Dong, Lihua Qiu, Xing Fan |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
High Energy Physics::Lattice
Science General Physics and Astronomy chemistry.chemical_element Fluorene 010402 general chemistry 01 natural sciences General Biochemistry Genetics and Molecular Biology Catalysis Rhodium Condensed Matter::Materials Science chemistry.chemical_compound Cascade reaction Computational chemistry Alkyne metathesis Physics::Chemical Physics lcsh:Science Multidisciplinary 010405 organic chemistry High Energy Physics::Phenomenology General Chemistry 0104 chemical sciences chemistry Axial chirality lcsh:Q Chirality (chemistry) Carbene |
| Zdroj: | Nature Communications, Vol 11, Iss 1, Pp 1-10 (2020) |
| ISSN: | 2041-1723 |
| DOI: | 10.1038/s41467-020-16098-8 |
| Popis: | In catalytic asymmetric reactions, the formation of chiral molecules generally relies on a direct chirality transfer (point or axial chirality) from a chiral catalyst to products in the stereo-determining step. Herein, we disclose a transient-axial-chirality transfer strategy to achieve asymmetric reaction. This method relies on transferring point chirality from the catalyst to a dirhodium carbene intermediate with axial chirality, namely a transient-axial-chirality since this species is an intermediate of the reaction. The transient chirality is then transferred to the final product by C(sp2)-H functionalization reaction with exceptionally high enantioselectivity. We also generalize this strategy for the asymmetric cascade reaction involving dual carbene/alkyne metathesis (CAM), a transition-metal-catalyzed method to access chiral 9-aryl fluorene frameworks in high yields with up to 99% ee. Detailed DFT calculations shed light on the mode of the transient-axial-chirality transfer and the detailed mechanism of the CAM reaction. |
| Databáze: | OpenAIRE |
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