Gold-Catalyzed Cyclizations of (<i>o</i>‑Alkynyl)phenoxyacrylates with External Nucleophiles: Regio- and Stereoselective Synthesis of Functionalized Benzo[<i>b</i>]oxepines

A catalytic approach to benzo[<i>b</i>]oxepines with high stereoselectivity by Au-catalyzed cyclization of (<i>o</i>-alkynyl)phenoxyacrylates with various nucleophiles under mild reaction conditions has been developed. Notably, the use of vinyl ether instead of alcohol could afford the same benzoxepines. The reaction may proceed by Au-catalyzed oligomerization of vinyl ether to release the alcohol, which then reacts with (<i>o</i>-alkynyl)phenoxyacrylates to furnish the benzoxepines

Gold-Catalyzed Cyclizations of (<i>o</i>‑Alkynyl)phenoxyacrylates with External Nucleophiles: Regio- and Stereoselective Synthesis of Functionalized Benzo[<i>b</i>]oxepines

A catalytic approach to benzo[<i>b</i>]oxepines with high stereoselectivity by Au-catalyzed cyclization of (<i>o</i>-alkynyl)phenoxyacrylates with various nucleophiles under mild reaction conditions has been developed. Notably, the use of vinyl ether instead of alcohol could afford the same benzoxepines. The reaction may proceed by Au-catalyzed oligomerization of vinyl ether to release the alcohol, which then reacts with (<i>o</i>-alkynyl)phenoxyacrylates to furnish the benzoxepines

Gold-Catalyzed Intramolecular Indole/Alkyne Cyclization Cascades through a Heterolytic Fragmentation: 1,5-Indole Migration and Allenylation

Gold-catalyzed intramolecular reactions of 3-alkynyl-bearing indoles with diol groups lead to the formation of highly functionalized 3-allenylindoles with high efficiency. The reaction likely proceeds by a new gold-catalyzed cascade cyclization/heterolytic fragmentation/elimination reactions, which results in 1,5-indole migration and C-3 allenylation of indole moiety

Highly Stereoselective Synthesis of Trisubstituted cis-[3]Cumulenols from Alkynylated Oxatitanacycles in the Presence of Lewis acids

A highly efficient and stereoselective method for the synthesis of trisubstituted cis-[3]cumulenols via oxatitanacycles derived from titanium-mediated coupling of 1,3-butadiynes with aldehydes or ketones promoted by Lewis-acids is described

Highly Stereoselective Synthesis of Trisubstituted cis-[3]Cumulenols from Alkynylated Oxatitanacycles in the Presence of Lewis acids

A highly efficient and stereoselective method for the synthesis of trisubstituted cis-[3]cumulenols via oxatitanacycles derived from titanium-mediated coupling of 1,3-butadiynes with aldehydes or ketones promoted by Lewis-acids is described

Direct Reaction of Aroyl Cyanides with Azazirconacyclopentadienes: Synthesis and Structural Characterization of Stabilized Azazirconacyclopentenes

The direct reaction of aroyl cyanide with azazirconacyclopentadiene takes place at room temperature in THF. The X-ray crystal structure analysis of the product 2e shows a novel azazirconacycle with a bidentate O−C−N unit. Hydrolysis of the newly formed zirconacycle affords the N-substituted benzamide derivative in good yield

Electrophilic Cyclization of 2-(1-Alkynyl)-2-alken-1-ones Using the I₂/K₃PO₄ System: An Efficient Synthesis of Highly Substituted Iodofurans

The electrophilic cyclization of 2-(1-alkynyl)-2-alken-1-ones in the presence of various alcohols or carbon-based nucleophiles offers an efficient and straightforward route to highly substituted iodofurans under extremely mild reaction conditions. The iodo derivatives are potential synthetic intermediates for amplification of molecular complexity

Gold-Catalyzed Intramolecular Indole/Alkyne Cyclization Cascades through a Heterolytic Fragmentation: 1,5-Indole Migration and Allenylation

Gold-catalyzed intramolecular reactions of 3-alkynyl-bearing indoles with diol groups lead to the formation of highly functionalized 3-allenylindoles with high efficiency. The reaction likely proceeds by a new gold-catalyzed cascade cyclization/heterolytic fragmentation/elimination reactions, which results in 1,5-indole migration and C-3 allenylation of indole moiety

Gold-Catalyzed Cyclizations of (<i>o</i>‑Alkynyl)phenoxyacrylates with External Nucleophiles: Regio- and Stereoselective Synthesis of Functionalized Benzo[<i>b</i>]oxepines

A catalytic approach to benzo[<i>b</i>]oxepines with high stereoselectivity by Au-catalyzed cyclization of (<i>o</i>-alkynyl)phenoxyacrylates with various nucleophiles under mild reaction conditions has been developed. Notably, the use of vinyl ether instead of alcohol could afford the same benzoxepines. The reaction may proceed by Au-catalyzed oligomerization of vinyl ether to release the alcohol, which then reacts with (<i>o</i>-alkynyl)phenoxyacrylates to furnish the benzoxepines

Direct Reaction of Aroyl Cyanides with Azazirconacyclopentadienes: Synthesis and Structural Characterization of Stabilized Azazirconacyclopentenes

The direct reaction of aroyl cyanide with azazirconacyclopentadiene takes place at room temperature in THF. The X-ray crystal structure analysis of the product 2e shows a novel azazirconacycle with a bidentate O−C−N unit. Hydrolysis of the newly formed zirconacycle affords the N-substituted benzamide derivative in good yield