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Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Photoinduced Reductive Coupling of Aliphatic Aldehydes with Vinyl/Alkynyl Halides to Access Allylic and Propargylic
Ruo-Ping Zheng1, Ting-Ting Miao1, Jun-Sheng Xu1
1College of Chemistry and Chemical Engineering and Key (Guangdong-Hong Kong Joint) Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou515063, P. R. China.
Abstract:
The synthesis of allylic and propargylic alcohols has traditionally relied on preformed organometallic reagents, stoichiometric metal reductants, or transition metal catalysts. Herein, we report a photoinduced, metal-free strategy that generates a ligated boryl radical in situ to activate aliphatic aldehydes, enabling their direct coupling with vinyl halides and alkynyl bromides to afford the corresponding allylic and propargylic alcohols. This method exhibits broad functional group tolerance and is applicable to the late-stage modification of complex molecules. Gram-scale synthesis and product derivatizations further demonstrate the synthetic utility of this protocol.
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