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Pd‐Catalyzed, Ligand‐Enabled Stereoselective 1,2‐Iodine(III) Shift/1,1‐Carboxyalkynylation of Alkynylbenziodoxoles
Author(s) -
Wu Junliang,
Xu Kai,
Hirao Hajime,
Yoshikai Naohiko
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201605772
Subject(s) - stereoselectivity , ligand (biochemistry) , catalysis , iodine , chemistry , enyne , coupling reaction , combinatorial chemistry , medicinal chemistry , stereochemistry , organic chemistry , biochemistry , receptor
A Pd II ‐catalyzed 2:1 coupling reaction of alkynylbenziodoxole with carboxylic acid to afford (alk‐1‐en‐3‐ynyl)benziodoxole, which is efficiently promoted by an octahydrophenazine ligand, is reported. The reaction involves a Pd‐assisted 1,2‐iodine(III) shift of the alkynylbenziodoxole followed by stereoselective introduction of carboxy and alkynyl groups (the latter originating from another molecule of the alkynylbenziodoxole) into the 1‐position of the transient Pd‐vinylidene species. The product of this 1,1‐carboxyalkynylation reaction serves as a new functionalized enyne‐type building block for further synthetic transformations.