Gold-Catalyzed Cyclizations of 4‑Alkyl-2-yn-1-yl (Oxy)cyclohexa-2,5-dien-1-ones (1) to Develop Two Cyclizations via π‑Alkyne versus π‑Allene Activations
Akshay Suresh Kshirsagar, Pei-Qin Liao, Tzuhsiung Yang, Rai-Shung Liu
TL;DR
This paper describes two new gold-catalyzed reactions that convert a specific compound into different products through distinct chemical pathways.
Contribution
The study introduces two novel gold-catalyzed cyclization pathways for a specific compound via π-alkyne and π-allene activations.
Findings
The π-allene route produces 2-substituted 3-formylbenzofurans via a [3.3] Claisen rearrangement mechanism.
The π-alkyne route stereoselectively forms C3,4-fused tetrahydrobenzofuran-5(4H)-ones using PhNH2 as a cocatalyst.
DFT calculations confirm the proposed mechanism involving water as a key player in the π-allene pathway.
Abstract
This work reports two new gold-catalyzed cyclizations of 4-alkyl-2-yn-1-yl (oxy)cyclohexa-2,5-dien-1-ones (1) via gold−π-allene versus gold−π-alkyne routes, The π-allene route involves a [3.3] Claisen rearrangement of 1-alloxyallene intermediates to enable a 1,3-group migration, ultimately affording 2-substituted 3-formylbenzofurans (2). Density functional theory (DFT) calculations support this proposed mechanism in which water plays a key role. An alternative π-alkyne route contains cocatalyst PhNH2 (10 mol %), leading to the formation of C3,4-fused tetrahydrobenzofuran-5(4H)-ones (3) stereoselectively.
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Taxonomy
TopicsCatalytic Alkyne Reactions · Sulfur-Based Synthesis Techniques · Cyclization and Aryne Chemistry