Dual Photoredox and Titanium Catalyzed Regioselective Allenylation of Aldehydes via Reductive Radical-Polar Crossover
Zulin Xiao
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
These authors contributed equally.
Search for more papers by this authorWenzhe Shang
Dalian University of Technology, School of Chemistry, Dalian, Liaoning, 116024 China
These authors contributed equally.
Search for more papers by this authorTao Huang
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
These authors contributed equally.
Search for more papers by this authorLei He
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
Search for more papers by this authorJingyao Li
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
Search for more papers by this authorShen Luo
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
Search for more papers by this authorXiaoxia He
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
Search for more papers by this authorXiang Li
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
Search for more papers by this authorCorresponding Author
Fusheng Li
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
E-mail: [email protected]Search for more papers by this authorZulin Xiao
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
These authors contributed equally.
Search for more papers by this authorWenzhe Shang
Dalian University of Technology, School of Chemistry, Dalian, Liaoning, 116024 China
These authors contributed equally.
Search for more papers by this authorTao Huang
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
These authors contributed equally.
Search for more papers by this authorLei He
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
Search for more papers by this authorJingyao Li
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
Search for more papers by this authorShen Luo
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
Search for more papers by this authorXiaoxia He
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
Search for more papers by this authorXiang Li
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
Search for more papers by this authorCorresponding Author
Fusheng Li
School of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan, 421001 China
E-mail: [email protected]Search for more papers by this authorComprehensive Summary
The direct reductive coupling of carbonyl compounds with propargyl halides is a powerful and reliable tool in the synthesis of α-allenols. However, stoichiometric metal reductants, harsh reaction conditions and a variety of additional additives are required in the traditional strategies. Additionally, the reactivity and regioselectivity control remains an elusive challenge. Herein, we developed the Ti-catalyzed regioselective reductive coupling of readily available aldehydes and racemic propargyl bromides to rapidly access a wide range of α-allenols. This method proceed efficiently in a reductive radical-polar crossover manner featuring mild conditions, excellent regioselectivity control, broad substrate scope, and eco-friendliness. Preliminary mechanistic studies support the radical-involved catalytic cycle. And the DFT calculations demonstrate that the regioselectivity is determined by the Zimmerman-Traxler-type transition states.
Supporting Information
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