Pd‐Catalyzed, Ligand‐Enabled Stereoselective 1,2‐Iodine(III) Shift/1,1‐Carboxyalkynylation of Alkynylbenziodoxoles

A PdII‐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 ste...

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Published inChemistry : a European journal Vol. 23; no. 7; pp. 1521 - 1525
Main Authors Wu, Junliang, Xu, Kai, Hirao, Hajime, Yoshikai, Naohiko
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 31.01.2017
Wiley Subscription Services, Inc
Subjects
alkynylation
carboxylic acid
Carboxylic acids
Catalysts
Chemical reactions
Chemistry
Chemistry, Multidisciplinary
Coupling
cross-coupling
hypervalent iodine
Iodine
Ligands
palladium
Physical Sciences
Science & Technology
Transformations
PALLADIUM
ACTIVATION
CONDENSATION
EBX
ALDEHYDES
C-H ALKYNYLATION
HYPERVALENT IODINE REAGENTS
DECARBOXYLATIVE ALKYNYLATION
CARBOXYLIC-ACIDS
PHOTOREDOX CATALYSIS
hypervalent iodine
cross-coupling
palladium
carboxylic acid
alkynylation
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Summary:A PdII‐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. Shifty iodine: A PdII‐octahydrophenazine catalyst promotes 2:1 coupling of alkynylbenziodoxole with carboxylic acid. The reaction involves a PdII‐assisted 1,2‐iodine(III) shift of the alkynylbenziodoxole followed by stereoselective introduction of carboxy and alkynyl groups 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.
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content type line 23
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201605772