| Autor: |
Wanjun Chen, Xinlong Yan, Lin Fan, Xu Guo, Jian Yang, Yiming Chen, Shaofang Zhou, Guodu Liu |
| Jazyk: |
angličtina |
| Rok vydání: |
2024 |
| Předmět: |
|
| Zdroj: |
Green Synthesis and Catalysis, Vol 5, Iss 4, Pp 282-289 (2024) |
| Druh dokumentu: |
article |
| ISSN: |
2666-5549 |
| DOI: |
10.1016/j.gresc.2023.08.004 |
| Popis: |
The construction of chiral quaternary carbon stereocenters is a significant challenge in asymmetric synthesis. Catalytic synthesis of these structures with trisubstituted allylic alcohols is highly important. However, most of the reported methodologies required noble transition-metals. Herein we reported the first highly asymmetric stereoselective synthesis of cyclopentanes bearing chiral quaternary carbon stereocenters of trisubstituted allylic siloxanes by reductive cyclization of all carbon 1,6-alkynones with the non-noble nickel catalysis of Ni(cod)2 with P-chiral monophosphine ligand (S)-BIDIME. Various multi-substituted functionalized cyclopentanes were obtained in high yields (up to 96%), excellent enantioselectivities (up to >99% ee) and perfect stereoselectivities (>99:1 E/Z). Thirty-two examples were successfully established for this method. Clarified mechanism studies were investigated first time by React-IR and DFT calculations to understand and explain the ligand-control of excellent enantio-stereoselectivity. Gram-scale reaction and control experiments were carried out. A new reaction design was proposed for further application of this type of catalysis. |
| Databáze: |
Directory of Open Access Journals |
| Externí odkaz: |
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