Gold(I)-Catalyzed 1,6-Enyne Single-Cleavage Rearrangements: The Complete Picture

Eduardo García-Padilla; Feliu Maseras; Antonio M Echavarren

doi:10.1021/acsorginorgau.3c00028

Gold(I)-Catalyzed 1,6-Enyne Single-Cleavage Rearrangements: The Complete Picture

ACS Org Inorg Au. 2023 Aug 20;3(5):312-320. doi: 10.1021/acsorginorgau.3c00028. eCollection 2023 Oct 4.

Authors

Eduardo García-Padilla^{1

2}, Feliu Maseras^{1

2}, Antonio M Echavarren^{1

2}

Affiliations

¹ Institute of Chemical Research of Catalonia (ICIQ-CERCA), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain.
² Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, C/Marcel·lí Domingo s/n, 43007 Tarragona, Spain.

Abstract

We identify the factors that rule the selectivity in single-cleavage skeletal rearrangements promoted by gold(I) catalysts. We find that stereoconvergence is enabled by a rotational equilibrium when electron-rich substituents are used. The anomalous Z-selective skeletal rearrangement is found to be due to electronic factors, whereas endo-selectivity depends on both steric and electronic factors.