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. 2022 Feb 4;12(3):1791-1796.
doi: 10.1021/acscatal.1c05147. Epub 2022 Jan 18.

Efficient Heterogeneous Copper-Catalyzed Alder-Ene Reaction of Allenynamides to Pyrrolines

Zhiyao Zheng  1 , Luca Deiana  2 , Daniels Posevins  1 , Abdolrahim A Rafi  2 , Kaiheng Zhang  2 , Magnus J Johansson  3 , Cheuk-Wai Tai  4 , Armando Córdova  2 , Jan-E Bäckvall  1   2
Affiliations

Efficient Heterogeneous Copper-Catalyzed Alder-Ene Reaction of Allenynamides to Pyrrolines

Zhiyao Zheng et al. ACS Catal. .

Abstract

Herein, we describe an efficient nanocopper-catalyzed Alder-ene reaction of allenynamides. The copper nanoparticles were immobilized on amino-functionalized microcrystalline cellulose. A solvent-controlled chemoselectivity of the reaction was observed, leading to the chemodivergent synthesis of pyrrolines (2,5-dihydropyrroles) and pyrroles. The heterogeneous copper catalyst exhibits high efficiency and good recyclability in the Alder-ene reaction, constituting a highly attractive catalytic system from an economical and environmental point of view.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Cycloisomerization and Oxidative Carbocyclization of Allenynes: (a) [Rh], Ref (8); [Pt], [Au], and [Ag], Ref (9). (b) Refs (10f)–. (c) This Work
Scheme 2
Scheme 2. General Procedure for the Synthesis of Cu-AmP-MCC Catalyst
Figure 1
Figure 1
STEM bright-field images of Cu-AmP-MCC catalyst, (a) with 50 nm scale bar and (b) with 20 nm scale bar. Moiré fringes given by overlapping of crystalline particles are observed.
Scheme 3
Scheme 3. Regioselective and Divergent Synthesis of 4 and 5 from Allenynamides 3
Reaction conditions: 3 (0.20 mmol), Cu-AmP-MCC (5.4 mol %), Cs2CO3 (0.40 mmol), toluene (2.0 mL) or CHCl3 (2.0 mL), 80 °C, 24 h.
Figure 2
Figure 2
Recycling experiments of Cu-AmP-MCC-catalyzed reaction of 3a to Alder-ene product 4a
Scheme 4
Scheme 4. Deuterium-Labeling Experiments: (a) D2O as Additive and (b) Deuterated Substrate with H2O as Additive
Scheme 5
Scheme 5. Proposed Mechanism for the Copper-Catalyzed Alder-Ene Reaction of Allenynamides 3
See this image and copyright information in PMC

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