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Ruthenium(0) Catalyzed Endiyne-?-Ketol [4 + 2] Cycloaddition: Convergent Assembly of Type II Polyketide Substructures via C-C Bond Forming Transfer Hydrogenation.

ABSTRACT: Upon exposure of 3,4-benzannulated 1,5-diynes (benzo-endiynes) to ?-ketols (?-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 ?-ketol mediated transfer hydrogenolysis. This process provides a new, convergent means of assembling Type II polyketide substructures.

SUBMITTER: Saxena A 

PROVIDER: S-EPMC4470559 | biostudies-literature | 2015 May

REPOSITORIES: biostudies-literature

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Ruthenium(0) Catalyzed Endiyne-α-Ketol [4 + 2] Cycloaddition: Convergent Assembly of Type II Polyketide Substructures via C-C Bond Forming Transfer Hydrogenation.

Saxena Aakarsh A   Perez Felix F   Krische Michael J MJ  

Journal of the American Chemical Society 20150504 18

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  ...[more]

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