1362343-52-9Relevant academic research and scientific papers
Elucidating the mechanism of reversible oxiranations via magnetization transfer spectroscopy
Chase, Daniel T.,Moerdyk, Jonathan P.,Bielawski, Christopher W.
supporting information, p. 5510 - 5513 (2013/01/15)
The reversible [2 + 1] cycloadditions between an N,N′-diamidocarbene (DAC) and eight aldehydes were examined using NMR spectroscopy. Variable temperature magnetization transfer experiments revealed higher exchange rates and lower activation barriers when electron-deficient aldehydes were employed. Likewise, competitive equilibrium studies indicated a thermodynamic preference for electron-deficient aryl and sterically unhindered alkyl aldehydes compared to more electron-rich or bulkier substrates. Collectively, these and other data collected were consistent with the oxiranation process proceeding in an asynchronous manner.
Diamidocarbenes as versatile and reversible [2+1] cycloaddition reagents
Moerdyk, Jonathan P.,Bielawski, Christopher W.
scheme or table, p. 275 - 280 (2012/06/18)
We describe the synthesis of a variety of cyclopropanes and epoxides by combining a readily accessible and isolable N,N-2-diamidocarbene with a range of structurally and electronically diverse olefins and aldehydes, including electron-rich derivatives. Surprisingly, the cyclopropanation and epoxidation reactions were discovered to be rapid and thermally reversible at relatively low temperatures, two features often desired for applications that utilize dynamic covalent chemistry. In addition, a diamidocyclopropane derivative prepared via this method was hydrolysed successfully to form the corresponding linear carboxylic acid in a metal-and carbon monoxide-free hydrocarboxylation reaction. As such, diamidocarbenes are expected to find utility in the synthesis of cyclopropanes, epoxides and their derivatives, as well as in dynamic covalent chemistry applications.
