研究目的
To develop a regiodivergent hydroaminoalkylation of alkynes and allenes using a combined rhodium and photoredox catalytic system for synthesizing branched or linear homoallylic amines selectively.
研究成果
The developed Rh/photoredox dual catalysis system enables regiodivergent α-allylation of amines with alkynes and allenes, providing access to both branched and linear homoallylic amines with good to excellent yields and selectivity. This atom-economic method complements traditional allylation reactions and may inspire further transformations in organic synthesis.
研究不足
Dialkyl substituted alkynes were not successful substrates. Some substrates with meta-position electron-withdrawing groups did not react. Yields varied, and diastereoselectivity for branched products was moderate (1:1 to 3.2:1). The reaction is not subject to a radical-chain propagation mechanism, as indicated by low quantum yields.
1：Experimental Design and Method Selection:
The study employed a dual catalytic system combining rhodium catalysis and photoredox catalysis. The methodology involved screening various ligands, acids, solvents, and catalyst loadings to optimize reaction conditions for regiodivergent α-allylation of amines with alkynes and allenes. Theoretical models include radical pathways and oxidative quenching processes.
2：Sample Selection and Data Sources:
Substrates used include N-aryl tetrahydroisoquinolines, 1-aryl-1-propynes, and terminal allenes with various substituents. Selection criteria were based on electronic properties and functional group tolerance.
3：List of Experimental Equipment and Materials:
Equipment includes blue LED strips for irradiation, NMR spectroscopy for yield and selectivity determination. Materials include [Rh(cod)Cl]2, DPEphos, rac-BINAP, [Ir(ppy)2(dtbbpy)]PF6, various acids (e.g., PhMe2CCO2H, PPTS), solvents (DCE, DMF), and internal standards like 1,1,2,2-tetrachloroethane.
4：Experimental Procedures and Operational Workflow:
Reactions were conducted in solvent mixtures under irradiation with blue LED strips at room temperature. Procedures involved mixing substrates with catalysts and additives, irradiating for specified times, and analyzing crude mixtures via NMR. Control experiments were performed to verify the necessity of each component.
5：Data Analysis Methods:
Yields and regioselectivities were determined by 1H NMR spectroscopy using internal standards. Mechanistic studies included radical trapping experiments, Stern-Volmer plots, and light on/off experiments.
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