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Palladium‐Catalyzed [2+1] Cycloadditions Affording Vinylidenecyclopropanes as Precursors of 7‐Membered Carbocycles
Author(s) -
Lepronier Aymeric,
Achard Thierry,
Giordano Laurent,
Tenaglia Alphonse,
Buono Gérard,
Clavier Hervé
Publication year - 2016
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.201500971
Subject(s) - palladium , chemistry , cycloaddition , phosphine , catalysis , propargyl , medicinal chemistry , ring (chemistry) , denticity , organic chemistry , crystal structure
Palladium(II) acetate in association with secondary phosphine oxides provides an efficient catalytic system for [2+1] cycloadditions starting from oxanorbornene derivatives and tertiary propargyl esters giving rise to vinylidenecyclopropanes. This reaction is specific to bidentate phosphinito–phosphinous acid ligands generated from secondary phosphine oxides. The [2+1] cycloaddition was found broad in scope with a high tolerance to various functional groups. Moreover, vinylidenecyclopropanes were straightforwardly converted into oxabicyclo[3.2.1]oct‐2‐ene derivatives through a palladium‐catalyzed ring‐expansion. Finally, the oxa bridge cleavage of oxatricyclic compounds yields functionalized 7‐membered carbocycles.