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DOI: 10.1055/a-2109-1642
Gold(I)-Catalyzed Dearomatization–Allenene Reaction for the Construction of Polycycles with Excellent Diastereoselectivity
This work was supported by the Deutsche Forschungsgemeinschaft (DFG; HA 2973/17-1).
Abstract
The synthesis of complex polycycles starting from simple building blocks in just a few reaction steps is usually very challenging. Herein, we present the gold(I)-catalyzed synthesis of various polycycles via the dearomatization–allenene reaction of aryl propargyl ethers with different nucleophiles. Depending on the starting material, polycycles can be isolated in yields up to 94% and with an enantiomeric excess of 95%. Quantum chemical calculations show that for all starting materials a Claisen rearrangement to the allenene occurs in the first reaction sequence. The subsequent cyclization and reaction with a nucleophile leads to various polycycles with the formation of up to six new C–C bonds in only one reaction step. All reactions proceed with excellent diastereoselectivity, with an α-quaternary carbonyl carbon present in the products.
Key words
C–C bond-forming reactions - DFT calculations - allenenes - gold catalysis - polycycles - diastereoselectivitySupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2109-1642.
- Supporting Information
Publication History
Received: 27 April 2023
Accepted after revision: 12 June 2023
Accepted Manuscript online:
12 June 2023
Article published online:
10 July 2023
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