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

Junliang Wu; Kai Xu; Hajime Hirao; Naohiko Yoshikai

doi:10.1002/chem.201605772

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

Junliang Wu, Kai Xu, Hajime Hirao, Naohiko Yoshikai

Research output: Contribution to journal › Article › peer-review

22 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	1521-1525
Number of pages	5
Journal	Chemistry - A European Journal
Volume	23
Issue number	7
DOIs	https://doi.org/10.1002/chem.201605772
Publication status	Published - 2017 Jan 31
Externally published	Yes

Keywords

alkynylation
carboxylic acid
cross-coupling
hypervalent iodine
palladium

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/chem.201605772

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title = "Pd-Catalyzed, Ligand-Enabled Stereoselective 1,2-Iodine(III) Shift/1,1-Carboxyalkynylation of Alkynylbenziodoxoles",

abstract = "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.",

keywords = "alkynylation, carboxylic acid, cross-coupling, hypervalent iodine, palladium",

author = "Junliang Wu and Kai Xu and Hajime Hirao and Naohiko Yoshikai",

note = "Funding Information: This work was funded by the Singapore Ministry of Education (Singapore) and Nanyang Technological University (RG 3/15). We thank Drs. Rakesh Ganguly and Yongxin Li for their assistance with the X-ray crystallography. H.H. thanks the High-Performance Computing Centre of NTU for computer resources. Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2017",

month = jan,

day = "31",

doi = "10.1002/chem.201605772",

language = "English",

volume = "23",

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journal = "Chemistry - A European Journal",

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AU - Wu, Junliang

AU - Xu, Kai

AU - Hirao, Hajime

AU - Yoshikai, Naohiko

N1 - Funding Information: This work was funded by the Singapore Ministry of Education (Singapore) and Nanyang Technological University (RG 3/15). We thank Drs. Rakesh Ganguly and Yongxin Li for their assistance with the X-ray crystallography. H.H. thanks the High-Performance Computing Centre of NTU for computer resources. Publisher Copyright: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2017/1/31

Y1 - 2017/1/31

N2 - 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.

AB - 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.

KW - alkynylation

KW - carboxylic acid

KW - cross-coupling

KW - hypervalent iodine

KW - palladium

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DO - 10.1002/chem.201605772

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JO - Chemistry - A European Journal

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

Abstract

Keywords

ASJC Scopus subject areas

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