Organometallic transfer hydrometallation of unsaturated carbon-carbon bonds is an attractive way to prepare synthetically valuable organometallic reagents of higher complexity. Reactions utilizing inexpensive Grignard reagent as a sacrificial hydride source are particularly attractive; however, significant synthetic limitations exist. New methods have been reported recently by Thomas and coworkers showing the efficacy of iron catalysis for hydromagnesiation of vinyl arenes. Preliminary mechanistic information has been reported though reaction complexity and sensitivity have proved problematic toward developing a complete mechanistic picture. We present here kinetic studies using in situ infrared spectroscopy to acquire initial rates and complete time course data sets. The studies reveal the kinetic importance of transmetallation and kinetic transparency of beta-hydride elimination/alkene insertion. Limitations in the scope of vinyl arene are also explained.

Operando infrared spectroscopic studies of iron-catalyzed hydromagnesiation of vinyl arenes

255th National Meeting (2018)

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