钌（0）催化的烯二炔-α-酮醇[4 + 2]环加成反应：通过碳-碳键形成转移氢化反应对II型聚酮化合物亚结构进行汇聚式组装。
Ruthenium(0) Catalyzed Endiyne-α-Ketol [4 + 2] Cycloaddition: Convergent Assembly of Type II Polyketide Substructures via C-C Bond Forming Transfer Hydrogenation.
作者信息
Saxena Aakarsh, Perez Felix, Krische Michael J
机构信息
University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712, United States.
出版信息
J Am Chem Soc. 2015 May 13;137(18):5883-6. doi: 10.1021/jacs.5b02755. Epub 2015 May 4.
Abstract
Upon exposure of 3,4-benzannulated 1,5-diynes (benzo-endiynes) to α-ketols (α-hydroxyketones) in the presence of Ru(0) catalysts derived from Ru3(CO)12 and RuPhos or CyJohnPhos, successive redox-triggered C-C coupling occurs to generate products of [4 + 2] cycloaddition. The proposed catalytic mechanism involves consecutive alkyne-carbonyl oxidative couplings to form transient oxaruthanacycles that suffer α-ketol mediated transfer hydrogenolysis. This process provides a new, convergent means of assembling Type II polyketide substructures.
摘要
在由Ru₃(CO)₁₂与RuPhos或CyJohnPhos衍生的Ru(0)催化剂存在下，将3,4-苯并稠合的1,5-二炔（苯并-二炔）暴露于α-酮醇（α-羟基酮）中时，会发生连续的氧化还原引发的C-C偶联反应，生成[4 + 2]环加成产物。所提出的催化机理涉及炔烃-羰基的连续氧化偶联，形成瞬态氧杂钌环，该瞬态氧杂钌环会发生α-酮醇介导的转移氢解反应。这一过程提供了一种组装II型聚酮化合物亚结构的新的汇聚方法。
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