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π-Cu(ii)配合物催化的烯丙基2-萘基醚的对映选择性芳香克莱森重排反应

Enantioselective aromatic Claisen rearrangement of allyl 2-naphthyl ethers catalyzed by π-Cu(ii) complexes.

作者信息

Yao Lu, Takeda Kazuki, Ando Kaori, Ishihara Kazuaki

机构信息

Graduate School of Engineering, Nagoya University B2-3(611) Furo-cho, Chikusa Nagoya 464-8603 Japan

Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University Gifu 501-1193 Japan

出版信息

Chem Sci. 2023 Jan 20;14(9):2441-2446. doi: 10.1039/d2sc06771d. eCollection 2023 Mar 1.

DOI:10.1039/d2sc06771d
PMID:36873835
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9977442/
Abstract

The first catalytic enantioselective aromatic Claisen rearrangement of allyl 2-naphthyl ethers using 5-10 mol% of π-copper(ii) complexes is reported. A Cu(OTf) complex with an l-α-homoalanine amide ligand gave ()-products in up to 92% ee. Conversely, a Cu(OSOCF) complex with an l--leucine amide ligand gave ()-products in up to 76% ee. Density-functional-theory (DFT) calculations suggest that these Claisen rearrangements proceed stepwise tight-ion-pair intermediates, and that ()- and ()-products are enantioselectively obtained the staggered transition states for the cleavage of the C-O bond, which is the rate-determining step.

摘要

报道了使用5-10摩尔%的π-铜（II）配合物对烯丙基2-萘基醚进行的首例催化对映选择性芳香克莱森重排反应。一种带有L-α-高丙氨酸酰胺配体的Cu(OTf)配合物能以高达92%的对映体过量得到（）-产物。相反，一种带有L-亮氨酸酰胺配体的Cu(OSOCF)配合物能以高达76%的对映体过量得到（）-产物。密度泛函理论（DFT）计算表明，这些克莱森重排反应通过紧密离子对中间体逐步进行，并且（）-和（）-产物是通过C-O键断裂的交错过渡态对映选择性地得到的，而C-O键断裂是速率决定步骤。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2d0/9977442/2dd07dceabdb/d2sc06771d-s6.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2d0/9977442/2dd07dceabdb/d2sc06771d-s6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2d0/9977442/6a50322b2f46/d2sc06771d-s1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c2d0/9977442/4709c04bf250/d2sc06771d-f1.jpg
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