Enantioselective [1,3] O-to-C rearrangement: dearomatization of alkyl 2-allyloxy/benzyloxy-1/3-naphthoates catalyzed by a chiral π-Cu(ii) complex

An unprecedented catalytic asymmetric [1,3] O-to-C rearrangement of alkyl 2-allyloxy/benzyloxy-1/3-naphthoates was realized under the catalysis of a chiral π-Cu(ii) complex (1-10 mol%). This dearomatization strategy provides facile access to highly functionalized β-naphthalenone derivatives bearing...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2019-02, Vol.10 (8), p.2259-2263
Main Authors: Yao, Lu, Ishihara, Kazuaki
Format: Article
Language:English
Subjects:
Catalysis
Chemistry
Crystallography
Enantiomers
X-ray diffraction
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Summary:An unprecedented catalytic asymmetric [1,3] O-to-C rearrangement of alkyl 2-allyloxy/benzyloxy-1/3-naphthoates was realized under the catalysis of a chiral π-Cu(ii) complex (1-10 mol%). This dearomatization strategy provides facile access to highly functionalized β-naphthalenone derivatives bearing an all-carbon quaternary stereogenic center in high yield with excellent enantioselectivity. The π-cation interaction between the aromatic substituent of the ligand and the Cu(ii) center was proved by X-ray diffraction analysis and shown to be crucial for enantioselective control. Further preliminary mechanistic studies suggest that this intramolecular reaction proceeds through a contact ion pair intermediate.
ISSN:2041-6520
2041-6539
DOI:10.1039/c8sc05601c