Generation and utility of cyclic dienyl gold carbene intermediates
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...
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| Main Authors: | , , , , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
22 March 2023
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| In: |
ACS catalysis
Year: 2023, Volume: 13, Issue: 7, Pages: 4646-4655 |
| ISSN: | 2155-5435 |
| DOI: | 10.1021/acscatal.2c06188 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acscatal.2c06188
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| Author Notes: | Cheng Zhang, Kemiao Hong, Shanliang Dong, Mengting Liu, Matthias Rudolph, Martin C. Dietl, Jian Yin, A. Stephen K. Hashmi, and Xinfang Xu |
| Summary: | 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. |
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| Item Description: | Gesehen am 25.05.2023 |
| Physical Description: | Online Resource |
| ISSN: | 2155-5435 |
| DOI: | 10.1021/acscatal.2c06188 |