Pd-Catalyzed Conversion of Alkynyl‑λ3‑iodanes to Alkenyl‑λ3‑iodanes via Stereoselective 1,2-Iodine(III) Shift/1,1-Hydrocarboxylation

Alkynyl-λ3-iodanes have been established as alkynyl cation equivalents for the alkynylation of carbon- and heteroatom-based nucleophiles. Herein, we report an unprecedented reaction mode of this compound class, which features a Pd­(II)-assisted 1,2-I­(III) shift of an alkynylbenziodoxole. A Pd­(II)...

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Published inJournal of the American Chemical Society Vol. 138; no. 29; pp. 9105 - 9108
Main Authors Wu, Junliang, Deng, Xiaozhou, Hirao, Hajime, Yoshikai, Naohiko
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 27.07.2016
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
EBX REAGENTS
MULTISUBSTITUTED FURANS
ORGANIC-SYNTHESIS
ROOM-TEMPERATURE
PALLADIUM
HYPERVALENT IODINE REAGENTS
C-H ALKYNYLATION
CARBOXYLIC-ACIDS
DECARBOXYLATIVE ALKYNYLATION
PHOTOREDOX CATALYSIS
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Summary:Alkynyl-λ3-iodanes have been established as alkynyl cation equivalents for the alkynylation of carbon- and heteroatom-based nucleophiles. Herein, we report an unprecedented reaction mode of this compound class, which features a Pd­(II)-assisted 1,2-I­(III) shift of an alkynylbenziodoxole. A Pd­(II) catalyst mediates this shift and the subsequent interception of the transient vinylidene species with carboxylic acid (1,1-hydro­carboxylation). The product of this stereoselective rearrangement–addition reaction, β-oxyalkenyl­benziodoxole, represents a novel and useful building block for further synthetic transformations.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b06247