Liu Zhengyi, Pan Yue, Zou Peng, Huang Hanchu, Chen Yali, Chen Yiyun
State Key Laboratory of Bioorganic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
Department of Chemistry, Shanghai University, 99 Shangda Road, Shanghai 200444, China.
Org Lett. 2022 Aug 19;24(32):5951-5956. doi: 10.1021/acs.orglett.2c02210. Epub 2022 Aug 5.
Here we report δ-C-H alkynylation to synthesize various δ-alkynols from iminophenylacetic acids. The hypervalent iodine-coordinated benziodoxole-alkoxyl-iminophenylacetic acid complex was the key intermediate and was characterized by X-ray crystallography for the first time. δ-C-H alkynylation is compatible with sensitive functional groups, including azides, aldehydes, and free alcohols, for the synthesis of δ-alkynols with diversified substituents in excellent regioselectivity. This reaction extends to δ-hydroxylalkene and δ-hydroxylnitrile synthesis, and the δ-alkynol products are easily derivatized to other valuable bifunctional building blocks.
在此，我们报道了通过δ-C-H炔基化反应从亚氨基苯乙酸合成各种δ-炔醇。高价碘配位的苯并碘恶唑-烷氧基-亚氨基苯乙酸络合物是关键中间体，并且首次通过X射线晶体学对其进行了表征。δ-C-H炔基化反应与包括叠氮化物、醛和游离醇在内的敏感官能团兼容，能够以优异的区域选择性合成具有多样化取代基的δ-炔醇。该反应可扩展至δ-羟基烯烃和δ-羟基腈的合成，并且δ-炔醇产物易于衍生为其他有价值的双官能团结构单元。
