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Updated: Aug 8, 2025

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Enantioselective aromatic Claisen rearrangement of allyl 2-naphthyl ethers catalyzed by π-Cu(ii) complexes
Lu Yao1, Kazuki Takeda1, Kaori Ando2
1Graduate School of Engineering, Nagoya University B2-3(611) Furo-cho, Chikusa Nagoya 464-8603 Japan ishihara@cc.nagoya-u.ac.jp.
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.
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