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. 2023 Nov 24;25(46):8372-8376.
doi: 10.1021/acs.orglett.3c03511. Epub 2023 Nov 10.

Cobalt(I)-Catalyzed (3 + 2 + 2) Cycloaddition between Alkylidenecyclopropanes, Alkynes, and Alkenes

Eduardo Da Concepción  1 , Carlos Lázaro-Milla  1   2 , Israel Fernández  2 , José L Mascareñas  1 , Fernando López  1   3
Affiliations

Cobalt(I)-Catalyzed (3 + 2 + 2) Cycloaddition between Alkylidenecyclopropanes, Alkynes, and Alkenes

Eduardo Da Concepción et al. Org Lett. .

Abstract

Cobalt(I) catalysts equipped with bisphosphine ligands can be used to promote formal (3 + 2 + 2) intramolecular cycloadditions of enynylidenecyclopropanes of type 1. The method provides synthetically appealing 5,7,5-fused tricyclic systems in good yields and with complete diastereo- and chemoselectivity. Interestingly, its scope differs from that of previously reported annulations based on precious metal catalysts, specifically rhodium and palladium. Noticeably, density functional theory calculations confirm that the mechanism of the reaction is also different from those proposed for these other catalysts.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Previously Developed Related Intramolecular Cycloadditions of ACPs and This Work
Scheme 2
Scheme 2. Preliminary Tests Using Diyne 1a
Scheme 3
Scheme 3. Scope of the Co-Catalyzed (3 + 2 + 2) Annulation
Conditions: 1, CoBr2 (10 mol %), dppp (12 mol %), and Zn (50 mol %)/ZnBr2 (20 mol %) were heated in DCE at 110 °C for 16 h.
Scheme 4
Scheme 4. Synthetic Manipulation of the Cycloadducts
Figure 1
Figure 1
Computed reaction profile for reaction model of ACP 1p and [Co(dppp)]+. Relative free energies (ΔG, at 298 K) are given in kcal/mol. All data were computed at the PCM(DCE)-B3LYP-D3/def2-SVP level.
See this image and copyright information in PMC

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