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

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)2 complex with an L-α-homoalanine amide ligand gave (S)-products in up to 92% ee. Conversely, a Cu(OSO2C4F9)2 complex with an L-tert-leucine amide ligand gave (R)-products in up to 76% ee. Density-functional-theory (DFT) calculations suggest that these Claisen rearrangements proceed stepwise via tight-ion-pair intermediates, and that (S)- and (R)-products are enantioselectively obtained via the staggered transition states for the cleavage of the C–O bond, which is the rate-determining step.

Supplementary files

Article information

Article type
Edge Article
Submitted
08 Dec 2022
Accepted
19 Jan 2023
First published
20 Jan 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023, Accepted Manuscript

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

L. Yao, K. Takeda, K. Ando and K. Ishihara, Chem. Sci., 2023, Accepted Manuscript , DOI: 10.1039/D2SC06771D

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