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Palladium(II)‐Catalyzed Domino Reaction of 2‐(1‐Alkynyl)‐2‐alken‐1‐ones with Nucleophiles: Scope, Mechanism and Synthetic Application in the Synthesis of 3,4‐Fused Bicyclic Tetrasubstituted Furans
Author(s) -
Xiao Yuanjing,
Zhang Junliang
Publication year - 2009
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200800715
Subject(s) - nucleophile , chemistry , allylic rearrangement , bicyclic molecule , catalysis , olefin fiber , palladium , combinatorial chemistry , cascade reaction , coupling reaction , medicinal chemistry , stereochemistry , organic chemistry
Described herein is the development of a palladium(II)‐catalyzed two‐ or three‐component reaction of 2‐(1‐alkynyl)‐2‐alken‐1‐ones with nucleophiles and allylic chlorides. Various types of nucleophiles such as O‐ , N‐ , C ‐based nucleophiles and olefin‐tethered O‐ , N‐ , C ‐based nucleophiles were investigated. The scope, mechanism and application of this Pd(II)‐catalyzed domino reaction were studied. In these transformations, the palladium catalyst exhibits a dual role, serving simultaneously as a Lewis acid and a transition metal. Two possible reaction pathways (cross‐coupling reaction vs. Heck reaction) from the same intermediate furanylpalladium species were observed. The reaction pathway is dependent on the property of the nucleophile and the length of the tethered chain as well. When olefin‐tethered O ‐based nucleophiles were used, only the cross‐coupling reaction pathway was observed, in contrast, both reaction pathways were observed when olefin‐tethered C ‐based nucleophiles were employed. The product ratio is dependent on the length of the tethered chain. Furthermore, ring‐closing metathesis (RCM) of corresponding furans with CC bonds provides an easy method for the preparation of functionalized oxygen‐heterocycles – 3,4‐fused bicyclic furans. It is also noteworthy that allylic chloride can be as an oxidant besides its well known function as an alkylating reagent.