Synthesis of 3,4‐Dihalogenated Furan‐2‐(5 H)‐ones by Electrophilic Cyclization of 4‐Hydroxy‐2‐alkynoates

Functionalized 3,4‐dihalogenated furan‐2(5 H)‐ones can be readily prepared in moderate to good yields by treating 4‐hydroxy‐4‐arylbut‐2‐ynoate derivatives with ICl, IBr, and I₂. Both halogen atoms of the electrophile are incorporated in the product. The resulting halides can further afford polycyclic aromatic compounds using known palladium‐catalyzed coupling reactions.     

A new approach to the synthesis of 2-vinylthiophenes and selenophenes; competition between free radical and anionic cycloaromatization of bridged di- and tetrapropargylic sulfides and selenides

A series of unknown di- and tetrapropargylic sulfides and selenides have been prepared. In the presence of t-BuOK in dry THF these compounds underwent isomerization to the corresponding diallenes, followed by a tandem anionic cyclization and aromatization to 2-vinylthiophene or selenophene derivatives. Some mechanistic studies indicated competition between free radical and anionic cycloaromatization. The latter is influenced by the nature of the bridging heteroatom, substitution of the allenyl group and base concentration.     

Rhodium‐Catalyzed Hydroformylation of 1,1‐Disubstituted Allenes Employing the Self‐Assembling 6‐DPPon System

A rhodium‐catalyzed hydroformylation of 1,1‐disubstituted allenes is reported. Using a Rh^I/6‐DPPon catalyst system, one can obtain β,γ‐unsaturated aldehydes in high regio‐ and chemoselectivity. The Z‐configured product is formed with up to >95 % selectivity when unsymmetrically 1,1‐disubstituted allenes are submitted to the reaction conditions. This is the first time that these interesting building blocks are accessible by hydroformylation of allenes. The utility of this methodology is demonstrated by further transformations of one of the obtained products.     

Olefin‐Directed Palladium‐Catalyzed Regio‐ and Stereoselective Oxidative Arylation of Allenes

An olefin‐directed palladium‐catalyzed oxidative regio‐ and stereoselective arylation of allenes to afford 1,3,6‐trienes has been established. A number of functionalized allenes, including 2,3‐ and 3,4‐dienoates and 3,4‐dienol derivatives, have been investigated and found to undergo the olefin‐directed allene arylation. The olefin moiety has been proven to be a crucial element for the arylating transformation.