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

ABSTRACT: 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.

SUBMITTER: Yao L

PROVIDER: S-EPMC6385897 | biostudies-other | 2019 Feb

REPOSITORIES: biostudies-other

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

Yao Lu L Ishihara Kazuaki K

Chemical science 20190110 8

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 ...[more]

PMID: 30881650

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