Carbodiimide and Isocyanate Hydroboration by a Cyclic Carbodiphosphorane Catalyst

We report hydroboration of carbodiimide and isocyanate substrates catalyzed by a cyclic carbodiphosphorane catalyst. The cyclic carbodiphosphorane outperformed the other Lewis basic carbon species tested, including other zerovalent carbon compounds, phosphorus ylides, an N-heterocyclic carbene, and an N-heterocyclic olefin. Hydroborations of seven carbodiimides and nine isocyanates were performed at room temperature to form N-boryl formamidine and N-boryl formamide products. Intermolecular competition experiments demonstrated the selective hydroboration of alkyl isocyanates over carbodiimide and ketone substrates. DFT calculations support a proposed mechanism involving activation of pinacolborane by the carbodiphosphorane catalyst, followed by hydride transfer and B-N bond formation.PMID:37847813 | DOI:10.1002/chem.202303095

Source: Chemistry - October 17, 2023 Category: Chemistry Authors: Ben A Janda Julie A Tran Daniel K Chang Gabriela C Nerhood O Maduka Ogba Allegra L Liberman-Martin Source Type: research