A boryl-migratory semipinacol rearrangement  

作　　者：Dong-Hang Tan Zhi-Hao Chen Ling Yang Chang-Ting Li Fang-Hai Tu Qingjiang Li Honggen Wang 

机构地区：[1]Guangdong Key Laboratory of Chiral Molecule and Drug Discovery,School of Pharmaceutical Sciences,Sun Yat-sen University,Guangzhou 510006,China [2]State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources,School of Chemistry and Pharmaceutical Sciences of Guangxi Normal University,Guilin 541004,China

出　　处：《Science China Chemistry》2022年第4期746-752,共7页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22022114,21971261);the Key Project of Chinese National Programs for Fundamental Research and Development(2016YFA0602900);the Guang-dong Basic and Applied Basic Research Foundation(2020A1515010624);the Fundamental Research Funds for the Central Universities(20ykzd12);the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01Y093);the China Postdoctoral Science Foundation(2021M69360)。

摘　　要：The semipinacol rearrangement is one of the classic yet useful synthetic tools in organic synthesis.However,semipinacol rearrangements involving heteroatom-migration are rare.Reported herein is a boryl-migratory semipinacol rearrangement of α-hydroxyallylboronates and α-hydroxypropargylboronates triggered by diverse halogen-,oxygen-,sulfur-and seleniumcontaining electrophiles.The protocol leads to a mild and facile access to organoborons bearing valuable functionalities.The σ(C-B)hyperconjugation is believed to be the key factor that leads to the observed exclusive chemoselectivity and enhanced reactivity.Synthetic utilities of the formed products were demonstrated.

关 键 词：1 2-boryl migration HYPERCONJUGATION iterative cross-coupling organoborons semipinacol rearrangement sp3-B tetrasubstituted alkene 

分 类 号：O621.259.3[理学—有机化学]