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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

By Aakarsh Saxena (1602616), Felix Perez (1447528) and Michael J. Krische (1324470)

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 Ru<sub>3</sub>(CO)<sub>12</sub> 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

Topics: Biophysics, Biochemistry, Cell Biology, Cancer, Environmental Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Ru, RuPho, presence, Transfer, CyJohnPho, Type II Polyketide Substructures, convergent, transfer hydrogenolysis, cycloaddition, Type II polyketide substructures, Ruthenium, Forming, mechanism, exposure, ketol, diyne, HydrogenationUpon, hydroxyketone, catalyst, oxidative, Catalyzed, Convergent Assembly, Bond, coupling, benzannulated, oxaruthanacycle, Endiyne, Cycloaddition
Year: 2015
DOI identifier: 10.1021/jacs.5b02755.s002
OAI identifier: oai:figshare.com:article/2167390
Provided by: FigShare
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