Main Reference
Jørgensen, L.; McKerrall, S. J.; Kuttruff, C. A.; Ungeheuer, F.; Felding, J.; Baran, P. S. Science 2013, 341, 878-882.

Garst, J. F.; Soriaga, M. P. Coord. Chem. Rev. 2003, 248, 623-652.

This paper looks at the driving mechanism behind the reaction of magnesium metal with organic halides in either solvents. The paper talks about how the Mg2+ is lost from the metal and leads to the halide being reduced. The paper discusses the reactions of Mg and the Grignard reagent with alkyl halides, cyclopropyl halides, vinyl halides, aryl halides and the intermediates that are formed. In most of the reactions, there would be a halide attached to the molecule and by reacting with the Mg, the Mg would become attached to the halide. In the intermediate, it can be seen that the halide takes one of the electrons from the bond between it and the carbon while the carbon keeps one of the electrons. The halide and Mg then form the bond with the carbon by contributing an electron each (one from the halide and one from the carbon). An example is given of the reaction between a phenyl radical with a phenyl-halide anion-radical or phenylmagnesium halide (shown below). Similar to our reaction, the group attached to the Mg becomes attached to the original molecule.

Storozhenko, P. A.; Grachev, A. A.; Klochkov, A. O.; Shiryaev, V. I. Russ. J. Appl. Chem. 2013, 86, 387-393.

The purpose of this paper was to work on finding new ways to produce these organoelemental compounds with environmentally friendly technologies. Part of the problem in their synthesis is the use of solvents that are very volatile and flammable. The low boiling points of these compounds, diethyl ether and THF for example, put limitations on the reaction between organohalides and magnesium to produce Grignard reagents, information which was cited from our “cool” paper. The paper goes on to explore other solvents which are less volatile and which do not put these magnesium/organohalides in an ether environment. 

Chen, Z.-N.; Fu, G.; Xu, X. Org. Lett. 2011, 13, 2046-2049.

            It is shown that two competitive pathways (T2 vs T4) exist for Grignard reagent formation. While the nonradical pathway T2 leads to retention of the configuration, the radical pathway T4 gives racemization. It is suggested that T2 can be enhanced, which should be of significance to prompt new synthesis approaches for the preparation of chiral Grignard reagents.
Our original paper used Grignard reaction to add two carbon using Grignard reagent, which should be fresh and prepared within a certain amount of time. If we instead want to add a more complicated substituent to the molecule, this finding can be extremely useful in eliminating byproducts.

Chen, ZN.; Fu, G.; Xu, X. Org. Biomol. Chem. 2012, 10, 9491-9500.

In this paper, the scientists discuss the mechanisms behind Grignard reagent formation between CH3Cl reacting with atoms and molecules containing Mg. The observed activity of the Mg atom at different states and conditions such as at ground state or excited state and under metal vapor synthesis conditions or matrix conditions. The scientists are performing this experiment in order to better understand the mechanisms behind the preparation of chiral Grignard reagents.

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