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 semip...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.展开更多
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)+3 种基金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)。
文摘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.
