Magnesium
Name Reactions
Recent Literature
An operationally simple and very efficient Reformatsky reaction of aldehydes has
been carried out in THF in the presence of low valent iron or copper which were
prepared in situ employing a bimetal redox strategy through reduction of Fe(III)
or Cu(II) salts with magnesium.
A. Chattopadhyay, A. Kr. Dubey, J. Org. Chem., 2007,
72, 9357-9359.
A user-friendly and operationally simple Ni-catalyzed carboxylation of
unactivated primary alkyl bromides and sulfonates with CO2 at
atmospheric pressure is characterized by its mild conditions and remarkably wide
scope without the need for air- or moisture-sensitive reagents.
Y. Liu, J. Cornella, R. Martin, J. Am. Chem. Soc., 2014,
136, 11212-11215.
An efficient Ni-catalyzed reductive carboxylation of brached and linear allylic
alcohols with CO2 provides linear β,γ-unsaturated carboxylic acids as
the sole regioisomer with generally high E/Z stereoselectivity. In
addition, the carboxylic acids can be generated from propargylic alcohols via a
hydrogenation step made possible by a Ni hydride intermediate produced by 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.
A Ni-catalyzed regiodivergent reductive carboxylation of allyl esters with CO2
is mild, user-friendly, and operationally simple. The reaction is characterized
by an exquisite selectivity profile that is dictated by the ligand backbone.
T. Moragas, J. Cornella, R. Martin,
J. Am. Chem. Soc., 2014,
136, 17702-17705.
An intermolecular pinacol coupling of aromatic or aliphatic carbonyl
compounds catalyzed by a complex of samarium diiodide (SmI2) with
tetraglyme in the presence of Me2SiCl2 and Mg is
described. High diastereoselectivity has been achieved in reactions with
aliphatic and aromatic aldehydes. De values
of up to 99% have been achieved in intramolecular pinacol coupling reactions.
H. C. Aspinall, N. Greeves, C. Valla, Org. Lett., 2005, 7, 1919-1922.
Rieke Ni generated in situ was able to promote the pinacol coupling of
various carbonyls efficiently. Another catalytically effective, cheaper
and more convenient NiCl2(Cat.)/Mg/TMSCl system was designed
and developed further successfully. Single-electron transfer (SET)
mechanisms for the coupling reactions and the DL/meso
diastereoselectivity were also explained.
L. Shi, C.-A. Fan, Y.-Q. Tu, M. Wang, F.-M. Zhang, Tetrahedron,
2004, 60, 2851-2855.
Magnesium in methanol is an effective reagent for the chemoselective
reduction of ozonides and other peroxides. Mg/MeOH is significantly more
reactive than Me2S or PPh3 and somewhat more
reactive than Zn/HOAc.
P. Dai, P. H. Dussault, T. K. Trullinger, J. Org. Chem., 2004, 69, 2851-2852.
Mercury(II) chloride efficiently activates magnesium metal to induce a
desulfonylative trifluoromethylation process. The new reductive
trifluoromethylation provides an alternative method for efficient
trifluoromethylation of non-enolizable or enolizable aldehydes with readily
available phenyl trifluoromethyl sulfone reagent.
Y. Zhao, J. Zhu, C. Ni, J. Hu, Synthesis, 2010,
1899-1904.
Magnesium mediates a direct reductive carboxylation of easily prepared aryl
vinyl ketones to provide γ-keto carboxylic acids in good yields under an
atmosphere of carbon dioxide. The reaction offers eco-friendly reaction
conditions, a short reaction time and wide substrate scope and provided a useful
and convenient alternative to access biologically important γ-keto carboxylic
acids.
S. Zheng, T. Zhang, H. Maekawa, J. Org. Chem., 2022, 87,
7343-7349.
An operationally simple cross-coupling reaction between aryl halides and alkyl
halides with high selectivity utilizes CoCl2/Me4-DACH as a
catalyst system. The underlying domino process exhibits high sustainability as
it obviates the need for the pre-formation and handling of stoichiometric
amounts of hazardous Grignard compounds.
W. M. Czaplik, M. Mayer, A. J. von Wangelin, Synlett, 2009,
2931-2934.
A magnesium-mediated reductive cross-coupling between benzyl chlorides and aryl
chlorides or fluorides gives diarylmethanes in good to excellent yields in a
one-pot manner using easy-to-access mixed PPh3/NHC Ni(II) complexes
of Ni(PPh3)(NHC)Br2 as catalyst precursors.
J. Zhang, G. Lu, J. Xu, H. Sun, Q. Shen, Org. Lett.,
2016, 18, 2860-2863.
A low-valent titanium generated in situ from Ti(O-i-Pr)4,
Me3SiCl, and Mg powder in THF reacted with a broad range of sulfonamides in a reductive bond
cleaving pathway to provide the corresponding amines, hydrocarbons and thiols.
The reagent could also cleave sulfonates to the corresponding alcohols.
N. Shohji, T. Kawaji, S. Okamoto, Org. Lett., 2011,
13, 2626-2629.
A chromium-catalyzed activation of acyl C-O bonds with magnesium enables an
amidation of esters with nitroarenes in the presence of chlorotrimethylsilane as
additive. The reaction provides a step-economic strategy to the synthesis of
important amide motifs using inexpensive and air-stable nitroarenes as amino
sources.
L. Ling, C. Chen, M. Luo, X. Zeng,
Org. Lett., 2019, 21, 1912-1916.
