Gold(I)-Catalyzed Dearomatization–Allenene Reaction for the Construction of Polycycles with Excellent Diastereoselectivity

Nina Semleit; Gebhard Haberhauer

doi:10.1055/a-2109-1642

Synthesis, Table of Contents

Synthesis 2023; 55(24): 4080-4090
DOI: 10.1055/a-2109-1642

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Gold(I)-Catalyzed Dearomatization–Allenene Reaction for the Construction of Polycycles with Excellent Diastereoselectivity

Nina Semleit

,

Gebhard Haberhauer ∗

Abstract

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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 - diastereoselectivity

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References

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