| Autor: |
Keary Engle, Peng Liu, Indrawan McAlpine, Scott Sutton, Ru Zhou, Ryan Patman, Sajiv Nair, Alexander Burtea, Gary Gallego, Kane Xu, Tuğçe Erbay, Taeho Kang |
| Rok vydání: |
2020 |
| DOI: |
10.26434/chemrxiv.12788390 |
| Popis: |
A unified synthetic strategy to access tertiary four-membered carbo/heterocyclic boronic esters is reported. Use of a Cu(I) catalyst in combination with a modified dppbz ligand enables regioselective hydroboration of various substituted benzylidenecyclobutanes and carbo/heterocyclic analogs. The reaction conditions are mild, and the method tolerates a wide range of medicinally relevant heteroarenes. The protocol can be conveniently conducted on gram-scale, and the tertiary boronic ester products undergo facile diversification into valuable targets. Reaction kinetics and computational studies indicate that the migratory insertion step is turnover-limiting and accelerated by electron-withdrawing groups on the dppbz ligand. Energy decomposition analysis (EDA) calculations reveal that electron-deficient P-aryl groups on the dppbz ligand enhance the T-shaped π/π interactions with the substrate and stabilize the migratory insertion transition state. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
|
