Generation and utility of cyclic dienyl gold carbene intermediates

• Verfasst von: Zhang, Cheng [VerfasserIn]
• Verfasst von: Hong, Kemiao [VerfasserIn]
• Verfasst von: Dong, Shanliang [VerfasserIn]
• Verfasst von: Liu, Mengting [VerfasserIn]
• Verfasst von: Rudolph, Matthias [VerfasserIn]
• Verfasst von: Dietl, Martin C. [VerfasserIn]
• Verfasst von: Yin, Jian [VerfasserIn]
• Verfasst von: Hashmi, A. Stephen K. [VerfasserIn]
• Verfasst von: Xu, Xinfang [VerfasserIn]
• Titel: Generation and utility of cyclic dienyl gold carbene intermediates
• Verf.angabe: Cheng Zhang, Kemiao Hong, Shanliang Dong, Mengting Liu, Matthias Rudolph, Martin C. Dietl, Jian Yin, A. Stephen K. Hashmi, and Xinfang Xu
• E-Jahr: 2023
• Jahr: 22 March 2023
• Umfang: 10 S.
• Fussnoten: Gesehen am 25.05.2023
• Titel Quelle: Enthalten in: American Chemical SocietyACS catalysis
• Ort Quelle: Washington, DC : ACS, 2011
• Jahr Quelle: 2023
• Band/Heft Quelle: 13(2023), 7 vom: März, Seite 4646-4655
• ISSN Quelle: 2155-5435
• DOI: doi:10.1021/acscatal.2c06188
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1846215552

Abstract

Exploration of intermediates that enable chemo- and stereoselective cycloaddition reactions for the expeditious construction of fused- and bridged-ring systems continues to draw a great deal of interest from the synthetic community. Vinylcarbene intermediates, which serve as 1- or 3-carbon building blocks, have been frequently used for the construction of cyclic frameworks through the successive formation of multiple carbon-carbon or/and carbon-heteroatom bonds. Here, we present a concise strategy for the catalytic generation of cyclic dienyl gold carbene species (Au-CDC) via a selective gold-promoted diazo-enyne carbocyclization process. Following cycloadditions of these in situ formed carbene intermediates with different types of dipolarophiles are disclosed, producing a diverse array of fused and bridged skeletons with high chemo- and stereoselectivity. This method provides a tool resulting in straightforward access to ring systems with structural complexity and diversity, and is a substantial complementary protocol to existing methods relying on using open-chained vinylcarbene species. The subsequent exploration of these generated cyclopentadiene motifs with dipolarophiles in accessing targets of polycyclic structures can further increase this rings-per-operation count, leading conceptually to the Au-CDC as a key bridge capable of connecting back-to-back cycloadditions.