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Through-Space 1,4-Ni/H Shift: Unlocking Migration along Coupling Partners in Olefin Borylcarbofunctionalization
Wenqing Guo1, Letian Zi1, Jingjie Yang1
1State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
This study introduces a novel migratory coupling for alkene difunctionalization, enabling selective functionalization via a 1,4-Nickel/Hydride shift along the coupling partner. This method efficiently synthesizes alkyl boronates and allows for dual migration for complex cross-coupling reactions.
Area of Science:
- Organic Chemistry
- Organometallic Chemistry
Background:
- Olefin migratory functionalization typically involves migration along the alkene.
- Selective functionalization of remote C(sp3)-H bonds is challenging.
Purpose of the Study:
- To develop a new migratory coupling strategy for alkene difunctionalization.
- To achieve selective migration along the C(sp2) coupling partner.
Main Methods:
- Utilizing a through-space 1,4-Nickel/Hydride (Ni/H) shift.
- Employing a three-component reaction strategy.
- Integrating 1,2-Ni/H and 1,4-Ni/H shifts for dual migration.
Main Results:
- Demonstrated selective migration along the C(sp2) coupling partner, distinct from alkene migration.
- Efficiently constructed densely functionalized alkyl boronates.
- Achieved selective borylative remote C(sp3)-H/C(sp2)-H cross-coupling via dual migration.
Conclusions:
- The developed strategy offers a novel approach to migratory coupling.
- Provides a modular and efficient route to complex organoboron compounds.
- Expands the scope of remote C-H functionalization and cross-coupling reactions.
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