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Chiral Fe(ii) complex catalyzed enantioselective [1,3] O-to-C rearrangement of alkyl vinyl ethers and synthesis of chromanols and beyond.

ABSTRACT: A highly efficient enantioselective [1,3] O-to-C rearrangement of racemic vinyl ethers that operates under mild conditions was developed. This method with chiral ferrous complex catalyst provided an efficient access to a wide range of chromanols with high yields and excellent enantioselectivities. In addition, an important urological drug (R)-tolterodine and others were easily obtained after simple transformations.

SUBMITTER: Wang L

PROVIDER: S-EPMC8162448 | biostudies-literature |

REPOSITORIES: biostudies-literature

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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.

Project description: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.

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Lewis acid catalyzed [1,3]-sigmatropic rearrangement of vinyl aziridines.

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Enantioselective Synthesis of Alkyl Allyl Ethers via Palladium-Catalyzed Redox-Relay Heck Alkenylation of <i>O</i>-Alkyl Enol Ethers.

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Formation of Chiral Allylic Ethers via an Enantioselective Palladium-Catalyzed Alkenylation of Acyclic Enol Ethers.

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Enantioselective hydroformylation of N-vinyl carboxamides, allyl carbamates, and allyl ethers using chiral diazaphospholane ligands.

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Copper Hydride Catalyzed Enantioselective Synthesis of Axially Chiral 1,3-Disubstituted Allenes.

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Palladium-Catalyzed Selective ?-Alkenylation of Pyridylmethyl Ethers with Vinyl Bromides.

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