These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
4 files

Multifaceted Substrate–Ligand Interactions Promote the Copper-Catalyzed Hydroboration of Benzylidenecyclobutanes and Related Compounds

submitted on 12.08.2020, 04:30 and posted on 12.08.2020, 09:54 by Taeho Kang, Tuğçe Erbay, Kane Xu, Gary Gallego, Alexander Burtea, Sajiv Nair, Ryan Patman, Ru Zhou, Scott Sutton, Indrawan McAlpine, Peng Liu, Keary Engle
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.




Kwanjeong Educational Foundation Graduate Fellowship


Email Address of Submitting Author


The Scripps Research Institute



ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest to declare.