Iridium-Catalyzed 1,3-Rearrangement of Allylic Alcohols

被引：6

作者：

Li, Fei ^{[1
]}

Luo, Yicong ^{[1
]}

Zhu, Xuejie ^{[1
]}

Ye, Yong ^{[2
]}

Yuan, Qianjia ^{[1
]}

Zhang, Wanbin ^{[1
,2
]}

机构：

[1] Shanghai Jiao Tong Univ, Frontiers Sci Ctr Transformat Mol, Sch Chem & Chem Engn, Shanghai Key Lab Mol Engn Chiral Drugs, 800 Dongchuan Rd, Shanghai 200240, Peoples R China

[2] Zhengzhou Univ, Coll Chem, 75 Daxue Rd, Zhengzhou 450052, Henan, Peoples R China

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2023年 / 29卷 / 20期

基金：

中国国家自然科学基金; 国家重点研发计划;

关键词：

allylic alcohol; homoallylic alcohol; iridium; metal hydride; rearrangement; ASYMMETRIC HYDROGENATION; ENANTIOSELECTIVE HYDROGENATION; REARRANGEMENT; TRANSPOSITION; ALKYLATION; ACID; 1,3-ISOMERIZATION; ISOMERIZATION; COMPLEX; TANDEM;

D O I：

10.1002/chem.202300027

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The allylic alcohol structural motif is prevalent in many important molecules and valuable building blocks. The rearrangement reaction is one of the most important transformations, however there are only a few reports for the 1,3-rearrangement of allylic alcohols. Herein, a 1,3-rearrangement of allylic alcohols catalyzed by an Ir(III) dihydride complex is described. This reaction could provide the corresponding less accessible allylic alcohols regio- and stereoselectively from readily available E/Z mixtures of the substrates. Furthermore, a tandem alkene isomerization followed by 1,3-rearrangement of homoallylic alcohols was also realized. In addition, this rearrangement reaction could be used to synthesize the natural product Navenone B. Mechanistic investigation indicated that the reaction pathway involved a pi-allyl-Ir(V) intermediate and that the dihydride in the iridium catalyst acts as a hydrogen switch to modulate the valence of the iridium center.

引用

页数：6

共 61 条

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