TY - JOUR
T1 - Pd-Catalyzed Conversion of Alkynyl-λ3-iodanes to Alkenyl-λ3-iodanes via Stereoselective 1,2-Iodine(III) Shift/1,1-Hydrocarboxylation
AU - Wu, Junliang
AU - Deng, Xiaozhou
AU - Hirao, Hajime
AU - Yoshikai, Naohiko
N1 - Funding Information:
This work was funded by the 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.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/7/27
Y1 - 2016/7/27
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.6b06247
DO - 10.1021/jacs.6b06247
M3 - Article
AN - SCOPUS:84979900752
SN - 0002-7863
VL - 138
SP - 9105
EP - 9108
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 29
ER -