Magnesium

Product Manager

Sandra Forbes

Name Reactions

Pinacol Reaction

Grignard Reaction

Recent Literature

A straightforward and highly effective Reformatsky reaction of aldehydes has been executed in tetrahydrofuran (THF) utilizing low-valent iron or copper catalysts, which were generated in situ through a bimetallic redox approach involving the reduction of Fe(III) or Cu(II) salts with magnesium.
A. Chattopadhyay, A. Kr. Dubey, J. Org. Chem., 2007, 72, 9357-9359.

DOI: 10.1021/jo0710984

A Ni-catalyzed carboxylation of unactivated primary alkyl bromides and sulfonates with CO2 at atmospheric pressure features user-friendliness, operational simplicity, mild conditions, and a remarkably broad scope. This process does not require air- or moisture-sensitive reagents.
Y. Liu, J. Cornella, R. Martin, J. Am. Chem. Soc., 2014, 136, 11212-11215.

DOI: 10.1021/ja5064586

An efficient Ni-catalyzed reductive carboxylation of both branched and linear allylic alcohols with CO2 yields linear β,γ-unsaturated carboxylic acids exclusively, exhibiting generally high E/Z stereoselectivity. Furthermore, the carboxylic acids can be synthesized from propargylic alcohols through a hydrogenation step facilitated by a Ni hydride intermediate, which is generated via a hydrogen atom transfer from water.
Y.-G. Chen, B. Shuai, C. Ma, X.-J. Zhang, P. Fang, T.-S. Mei, Org. Lett., 2017, 19, 2969-2972.

DOI: 10.1021/acs.orglett.7b01208

The Ni-catalyzed reductive carboxylation of allyl esters with CO2 is a mild, user-friendly, and straightforward process. It is distinguished by its remarkable selectivity profile, which is determined by the ligand backbone.
T. Moragas, J. Cornella, R. Martin, J. Am. Chem. Soc., 2014, 136, 17702-17705.

DOI: 10.1021/ja509077a

A complex of samarium diiodide (SmI2) with tetraglyme, in the presence of Me2SiCl2 and magnesium, catalyzes an intermolecular pinacol coupling of aromatic or aliphatic carbonyl compounds. This process exhibits high diastereoselectivity when applied to aliphatic and aromatic aldehydes. Intramolecular pinacol coupling reactions have achieved de values as high as 99%.
H. C. Aspinall, N. Greeves, C. Valla, Org. Lett., 2005, 7, 1919-1922.

DOI: 10.1021/ol050256f

In situ generated Rieke Ni efficiently promoted the pinacol coupling of various carbonyl compounds. Furthermore, a more cost-effective and convenient NiCl2(Cat.)/Mg/TMSCl system was successfully designed and developed. Additionally, the mechanisms underlying the coupling reactions, involving single-electron transfer (SET), and the observed DL/meso diastereoselectivity were elucidated.
L. Shi, C.-A. Fan, Y.-Q. Tu, M. Wang, F.-M. Zhang, Tetrahedron, 2004, 60, 2851-2855.

DOI: 10.1016/j.tet.2004.01.073

Magnesium in methanol serves as an efficient reagent for the chemoselective reduction of ozonides and other peroxides, exhibiting significantly greater reactivity compared to Me2S or PPh3, and somewhat enhanced reactivity in comparison to Zn/HOAc.
P. Dai, P. H. Dussault, T. K. Trullinger, J. Org. Chem., 2004, 69, 2851-2852.

DOI: 10.1021/jo035191d

Mercury(II) chloride effectively activates magnesium metal to catalyze a desulfonylative trifluoromethylation reaction. This novel reductive trifluoromethylation offers an alternative approach for the efficient trifluoromethylation of both non-enolizable and enolizable aldehydes, utilizing the readily accessible phenyl trifluoromethyl sulfone reagent.
Y. Zhao, J. Zhu, C. Ni, J. Hu, Synthesis, 2010, 1899-1904.

DOI: 10.1055/s-0029-1218752

The employment of Mn/water facilitates a gentle and highly selective reduction of alkenes and alkynes. The precisely controlled production of H2 enables this selective reduction in the presence of labile functional groups, all under mild and environmentally benign conditions.
J. Rosales, T. Jiménez, R. Chahboun, M. A. Huertos, A. Millán, J. Justicia, Org. Lett., 2024, 26, 2147-2151.

DOI: 10.1021/acs.orglett.3c03664

Employing Mn/water allows for a gentle and highly selective reduction of alkenes and alkynes. By meticulously controlling the generation of H2, this method enables selective reduction in the presence of labile functional groups, all under mild and environmentally friendly conditions.
J. Rosales, T. Jiménez, R. Chahboun, M. A. Huertos, A. Millán, J. Justicia, Org. Lett., 2024, 26, 2147-2151.

DOI: 10.1021/acs.orglett.3c03664

Magnesium catalyzes a direct reductive carboxylation of readily prepared aryl vinyl ketones under a carbon dioxide atmosphere, yielding γ-keto carboxylic acids in good quantities. This reaction boasts eco-friendly conditions, a brief reaction time, and a broad substrate scope, providing a valuable and convenient alternative for synthesizing biologically significant γ-keto carboxylic acids.
S. Zheng, T. Zhang, H. Maekawa, J. Org. Chem., 2022, 87, 7343-7349.

DOI: 10.1021/acs.joc.2c00557

A straightforward cross-coupling reaction between aryl halides and alkyl halides, characterized by high selectivity, employs CoCl2/Me4-DACH as the catalyst system. This process showcases high sustainability, as it eliminates the requirement for the preliminary formation and manipulation of stoichiometric quantities of hazardous Grignard compounds.
W. M. Czaplik, M. Mayer, A. J. von Wangelin, Synlett, 2009, 2931-2934.

DOI: 10.1055/s-0029-1218012

Using readily accessible Ni(PPh3)(NHC)Br2 mixed PPh3/NHC Ni(II) complexes as catalyst precursors, a magnesium-mediated reductive cross-coupling between benzyl chlorides and aryl chlorides or fluorides yields diarylmethanes in good to excellent quantities in a one-pot procedure.
J. Zhang, G. Lu, J. Xu, H. Sun, Q. Shen, Org. Lett., 2016, 18, 2860-2863.

DOI: 10.1021/acs.orglett.6b01134

When generated in situ from Ti(O-i-Pr)4, Me3SiCl, and Mg powder in THF, low-valent titanium undergoes a reductive bond cleavage reaction with a wide variety of sulfonamides, yielding the corresponding amines, hydrocarbons, and thiols. Additionally, this reagent is capable of cleaving sulfonates to produce the corresponding alcohols.
N. Shohji, T. Kawaji, S. Okamoto, Org. Lett., 2011, 13, 2626-2629.

DOI: 10.1021/ol200740r

Chromium-catalyzed activation of acyl C-O bonds, facilitated by magnesium, allows for the amidation of esters with nitroarenes in the presence of chlorotrimethylsilane as an additive. This reaction offers a cost-effective strategy for synthesizing significant amide motifs, utilizing inexpensive and air-stable nitroarenes as amino sources.
L. Ling, C. Chen, M. Luo, X. Zeng, Org. Lett., 2019, 21, 1912-1916.

DOI: 10.1021/acs.orglett.9b00554

Quoted from:

https://www.organic-chemistry.org/chemicals/reductions/magnesium-mg.shtm

Aladdinsci: https://www.aladdinsci.com