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. 2023 Mar 8;145(9):4975-4981.
doi: 10.1021/jacs.3c00012. Epub 2023 Feb 22.

Generating Fischer-Type Rh-Carbenes with Rh-Carbynoids

Eric Palomo  1   2 , Akhilesh K Sharma  1 , Zhaofeng Wang  1 , Liyin Jiang  1 , Feliu Maseras  1 , Marcos G Suero  1
Affiliations

Generating Fischer-Type Rh-Carbenes with Rh-Carbynoids

Eric Palomo et al. J Am Chem Soc. .

Abstract

We describe the first catalytic generation of Fischer-type acyloxy Rh(II)-carbenes from carboxylic acids and Rh(II)-carbynoids. This novel class of transient donor/acceptor Rh(II)-carbenes evolved through a cyclopropanation process providing access to densely functionalized cyclopropyl-fused lactones with excellent diastereoselectivity. DFT calculations allowed the analysis of the properties of Rh(II)-carbynoids and acyloxy Rh(II)-carbenes as well as the characterization of the mechanism.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Generation of novel donor/acceptor Rh(II)-carbenes.
Figure 2
Figure 2
Mechanistic hypothesis.
Figure 3
Figure 3
Free energy profile for the catalyzed reaction between 1a and 2a* with Rh2(esp)2.
Figure 4
Figure 4
Computed geometry of Rh-carbynoid C with (a) side and (b) top views. For structural clarity, hydrogens are omitted, and carbon atoms are shown in tube format in the esp ligand.
See this image and copyright information in PMC

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