Manganese
Name Reactions
Recent Literature
An efficient, nickel-catalyzed direct reductive cross-coupling of equimolar
amounts of alkyl halides with aryl halides in the presence of manganese is
generally high-yielding, highly functional-group-tolerant, and easy to perform.
The reaction appears to avoid the formation of intermediate organomanganese
species, and a synergistic effect was found when a mixture of two ligands was
employed.
D. A. Everson, R. Shrestha, D. J. Weix, J. Am. Chem. Soc., 2010,
132, 920-921.
An operationally simple and user-friendly Ni-catalyzed reductive deaminative
arylation at unactivated sp3 carbon centers exhibits an excellent
chemoselectivity profile and broad substrate scope. The reaction has also been
used in the context of late-stage functionalization to reliably generate
structure diversity with amine-containing drugs.
R. Martin-Montero, Y. R. Yatham, H. Yin, J. Davies, R. Martin,
Org. Lett., 2019, 21, 2947-2951.
A direct cobalt-catalyzed vinylation of various aromatic halides using
β-halostyrene proceeded smoothly with a total retention of the double bond
configuration in the presence of triphenylphosphine as ligand. This procedure
offers a new route to the stereoselective synthesis of functionalized stilbenes.
A. Moncomble, P. Le Floch, A. Lledos, C. Gosmini, J. Org. Chem., 2012,
77, 5056-5062.
A Ni-catalyzed asymmetric reductive cross-coupling between vinyl bromides and
benzyl chlorides provides direct access to enantioenriched products bearing
aryl-substituted tertiary allylic stereogenic centers from simple, stable
starting materials. A broad substrate scope can be converted under mild reaction
conditions without pregeneration of organometallic reagents and the
regioselectivity issues commonly associated with allylic arylation.
A. H. Cherney, S. E. Reisman,
J. Am. Chem. Soc., 2014,
136, 14365-14366.
A ligand-controlled nickel migration/arylation enables a highly efficient remote
reductive cross-electrophile coupling. This general protocol allows the use of
abundant and bench-stable alkyl bromides and aryl bromides for the synthesis of
a wide range of structurally diverse 1,1-diarylalkanes in excellent yields and
high regioselectivities under mild conditions.
F. Chen, K. Chen, Y. Zhang, Y. He, Y.-M. Wang, S. Zhu, J. Am. Chem. Soc., 2017,
139, 13929-13935.
A nickel-catalyzed cross-electrophile coupling reaction between benzyl
alcohols and aryl halides is mediated by a low-valent titanium reagent generated
from TiCl4(2,6-lutidine) and manganese powder. The reaction afforded the
cross-coupled product in high yield.
T. Suga, Y. Ukaji, Org. Lett.,
2018, 20, 7846-7850.
A convenient electrophile-electrophile cross-coupling of carboxylic acid
derivatives and alkylpyridinium salts via C-N bond cleavage provides various
functionalized ketones in very good yields. Besides acid chlorides, carboxylic
acids were also employed as acylating agents.
F. T. Pulikottil, R. Pilli, R. V. Suku, R. Rasappan,
Org. Lett., 2020, 22, 2833-2837.
A nickel-catalyzed asymmetric reductive cross-coupling trifluoroalkylation of
acyl chlorides enables an enantioselective synthesis of α-trifluoromethylated
ketones. A one-pot reduction furnished alcohols bearing β-CF3-substituted
stereogenic carbons with excellent diastereoselectivity. The reactions offer
high yields/enantioselectivity, mild conditions, and good functional group
compatibility.
B.-B. Wu, J. Xu, K.-J. Bian, Q. Gao, X.-S. Wang, J. Am. Chem. Soc.,
2022, 144, 6543-6550.
A nickel-catalyzed reductive cross-coupling reaction of acyl chlorides with
racemic secondary α-trifluoromethyl bromides provides structurally interesting
chiral α-CF3 carbonyl compounds with great enantioselectivity and
good functional group tolerance.
J. Wu, H. Wu, X. Liu, Y. Zhang, G. Huang, C. Zhang, Org. Lett.,
2022, 24, 4322-4327.
A nickel complex of isoquinox promoted enantioselective conjugate arylation
and heteroarylation of enones using aryl and heteroaryl halides directly.
Experiments and calculations supported an insertion of an arylnickel(I) complex
to enones via an elementary 1,4-addition.
L. Zhang, M. Zhao, M. Pu, Z. Ma, J. Zhou, C. Chen, Y.-D. Wu, Y. R. Chi, J. S.
Zhou, J. Am. Chem. Soc.,
2022, 144, 20249-20257.
A remote functionalization strategy enables a Z-selective
synthesis of silyl enol ethers of (hetero)aromatic and aliphatic ketones via
Ni-catalyzed chain walking from a distant olefin site. Mechanistic data indicate that a Ni(I) dimer is formed under these conditions,
which serves as a catalyst resting state and, upon reaction with an alkyl
bromide, is converted to [Ni(II)-H] as active
catalyst.
S. Guven, G. Kundu, A. Wessels, J. S. Ward, K. Rissanen, F. Schoenebeck, J. Am. Chem. Soc.,
2021, 143, 8375-8380.
A nickel complex of a chiral bisoxazoline ligand catalyzed the
stereoselective reductive arylation of ketones in high enantioselectivity. A
range of common acyclic and cyclic ketones reacted without the aid of directing
groups.
S. Huang, J. S. Zhou, J. Am. Chem. Soc.,
2024, 146, 11895-112900.
A mild and convenient defluorinative reductive cross coupling of gem-difluoroalkenes
with aliphatic aldehydes provides diverse β-fluorinated allylic alcohols in good
yields. The reaction is operationally simple and shows good functional group
tolerance.
Y.-T. Liu, Y.-H. Fan, Y. Mei, D.-J. Li, Y. Jiang, W.-H. Yu, F. Pan, Org. Lett., 2023, 25,
549-554.
A nickel-catalyzed carboxylation of aryl and vinyl chlorides proceeds under a
CO2 pressure of 1 atm at room temperature in the presence of nickel
catalysts and Mn powder as a reducing agent. Various aryl chlorides and
vinyl chlorides could be converted to the corresponding carboxylic acid in good
yields.
T. Fujihara, K. Nogi, T. Xu, J. Terao, Y. Tsuji, J. Am. Chem. Soc., 2012,
134, 9106-9109.
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.
A catalytic carboxylation of unactivated primary, secondary, and tertiary alkyl
chlorides with CO2 at atmospheric pressure features exquisite
chemoselectivity, mild conditions and ease of execution.
M. Börjesson, T. Moragas, R. Martin, J. Am. Chem. Soc., 2016,
138, 7504-7507.
Nickel-catalyzed carboxylation of aryl fluorosulfates and heteroaryl
fluorosulfates with CO2 provides arene carboxylic acids in very good
yields under mild conditions. In addition, a one-pot phenol fluorosulfation/carboxylation
was developed.
C. Ma, C.-Q. Zhao, X.-T. Xu, Z.-M. Li, X.-Y. Wang, K. Zhang, T.-S. Mei,
Org. Lett., 2019, 21, 2464-2467.
In a NI-catalyzed protocol that reliably predicts and controls the
site-selective incorporation of CO2 to a wide range of unsaturated
hydrocarbons, water serves as formal hydride source.
M. Gaydou, T. Moragas, F. Juliá-Hernández, R. Martin, J. Am. Chem. Soc., 2017,
139, 12161-12164.
In a NI-catalyzed protocol that reliably predicts and controls the
site-selective incorporation of CO2 to a wide range of unsaturated
hydrocarbons, water serves as formal hydride source.
M. Gaydou, T. Moragas, F. Juliá-Hernández, R. Martin, J. Am. Chem. Soc., 2017,
139, 12161-12164.
An unprecedented cobalt-catalyzed highly site-, diastereo-, and
enantioselective protocol for stereoselective formation of nucleophilic
allyl-Co(II) complexes followed by addition to aldehydes provides diversified
enantioenriched homoallylic alcohols with a remarkably broad scope of allyl
groups that can be introduced.
L. Wang, L. Wang, M. Li, Q. Chong, F. Meng, J. Am. Chem. Soc.,
2021, 143, 12755-12765.
A Ni-catalyzed reductive deaminative cross-electrophile coupling reaction
between Katritzky salts and aromatic amides provides ketones. Due to mild
reaction conditions and high functional group tolerance, this cross-coupling
strategy is expected to be useful for late-stage functionalization of complex
compounds.
C.-G. Yu, Y. Matsuo,
Org. Lett., 2020, 22, 950-955.
A domino dehydrochlorination/Mn-enabled radical-based alkyl-alkyl
cross-coupling reaction allows a highly efficient alkylation of β-chloro
ketones via in situ-generated α,β-unsaturated ketones as reaction intermediates.
J. Wang, Y.-B. Pang, N. Tao, R.-S. Zeng, Y. Zhao, J. Org. Chem., 2019, 84,
15315-15322.
A highly efficient cobalt-catalyzed reductive carboxylation reaction of alkenyl
trifluoromethanesulfonates (triflates) enables the synthesis of α,β-unsaturated
carboxylic acids in the presence of Mn powder as a reducing reagent under 1 atm
pressure of CO2 at room temperature. Moreover, the carboxylation of
sterically hindered aryl triflates proceeds smoothly in the presence of a nickel
or cobalt catalyst.
K. Nogi, T. Fujihara, J. Terao, Y. Tsuji, J. Org. Chem.,
2015,
80, 11618-11623.
Unsymmetrical dialkyl ketones can be prepared by the nickel-catalyzed reductive
coupling of carboxylic acid chlorides or (2-pyridyl)thioesters with alkyl
iodides or benzylic chlorides. Various functional groups are tolerated,
including common nitrogen protecting groups and C-B bonds. Even hindered ketones
flanked by tertiary and secondary centers can be formed.
A. C. Wotal, D. J. Weix, Org. Lett., 2012,
14, 1363-1365.
A Ni-catalyzed three-component cross-electrophile coupling of 1,3-dienes with
aldehydes and aryl bromides using manganese metal as the reducing agent provides
1,4-disubstituted homoallylic alcohols.
Y.-Q. Qi, S. Liu, Y. Xu, Y. Li, T. Su, H.-L. Ni, Y. Gao, W. Yu, P. Cao, P. Hu,
K.-Q. Zhao, B.-Q. Wang, B. Chen, Org. Lett.,
2022, 24, 5023-5028.
An efficient and simple Cu-catalyzed Reformatsky reaction of carbonyl compounds
with ethyl iodoacetate provides excellent yields of β-hydroxyl esters using
inexpensive starting materials under mild reaction conditions.
L. Ouyang, J. H. Liao, Y. P. Xia, R. S. Luo, Synlett, 2020,
31,
1418-1422.
An enantioselective Ni-catalyzed reductive cross-coupling of acid chlorides
with racemic secondary benzyl chlorides in the presence of Mn0 as a stoichiometric reductant generates acyclic α,α-disubstituted ketones in good
yields and high enantioselectivity. The mild, base-free reaction conditions
tolerate various functional groups on both coupling partners.
A. H. Cherney, N. T. Kadunce, S. E. Reisman, J. Am. Chem. Soc., 2013,
135, 7442-7445.
A mild and user-friendly Ni-catalyzed regioselective hydrocarboxylation enables
a regioselective conversion of a broad range of alkynes with CO2 (1
bar) while obviating the need for sensitive organometallic species and using
simple alcohols as proton sources.
X. Wang, M. Nakajima, R. Martin, J. Am. Chem. Soc., 2015,
137, 8924-8927.
A generally applicable, sequential reaction of dichloroesters with various
aldehydes is promoted by active manganese to give α,β-unsaturated esters with
complete control of stereoselectivity. The C-C double bond can be di- or
trisubstituted. A mechanism based on a successive aldol-type reaction/-elimination
is proposed.
J. M. Concellón, H. Rodríquez-Solla, P. Díaz, R. Llaona, J. Org. Chem., 2007,
72, 4396-4400.
A complete E-selective synthesis of α,β-unsaturated amides through a
sequential reaction of a range of dichloroamides with a variety of aldehydes is
promoted by Rieke manganese (Mn*). The unsaturated amides obtained are readily
and efficiently transformed into α,β-unsaturated ketones, aldehydes, or
carboxylic acids.
J. M. Concellón, H. Rodríquez-Solla, P. Díaz, J. Org. Chem., 2007,
72, 7974-7979.
Stereoselective β-elimination of diastereomeric mixtures of
2-bromo-3-hydroxyesters is achieved by using unactivated manganese and
trimethylsilyl chloride, to yield (E)-α,β-unsaturated esters with total
diastereoselectivity.
J. M. Concellón, H. Rodríguez-Solla, V. del Amo, Synlett,
2006, 315-317.
A nickel-catalyzed asymmetric decarboxyarylation of NHP esters via reductive
cross-coupling provides structurally diverse chiral benzylamines. This method
has demonstrated excellent catalytic efficiency, high enantioselective control,
mild conditions, and good functional group tolerance.
C.-Y. Wang, Y.-L. Huang, W.-C. Xu, G. Gao, P. Liu, Y.-X. Bi, G.-K. Liu, X.-S.
Wang, Org. Lett., 2023, 25,
6925-6930.
A totally regioselective transformation of aromatic N-4-methoxyphenylaziridine
2-carboxamides into 2-aminoamides is promoted by active manganese (Mn*). α-Amino
ketones can be readily obtained by reaction of morpholine-derived 2-aminoamides
with organolithium compounds.
J. M. Concellón, H. Rodríguez-Solla, V. del Amo, P. Díaz, J. Org. Chem., 2010,
75, 2407-2410.
A Ni-catalyzed reductive carboxylation of N-substituted aziridines with
CO2 at atmospheric pressure provides β-amino acids, important
building blocks with considerable potential as peptidomimetics. The protocol
offers mild conditions, experimental ease, and exquisite chemo- and
regioselectivity.
J. Davies, D. Janssen-Müller, D. P. Zimin, C. S. Day, T. Yanagi, J. Elfert, R.
Martin, J. Am. Chem. Soc.,
2021, 143, 4949-4954.
A Cr-catalyzed asymmetric cross aza-pinacol coupling of aldehydes and N-sulfonyl
imines provides β-amino alcohols bearing vicinal stereocenters. This protocol
proceeds in a radical-polar crossover manner from the intermediacy of an α-amino
radical instead of a ketyl radical.
H. Hu, Z. Wang, J. Am. Chem. Soc.,
2023, 145, 20775-20781.
A nickel-catalyzed reductive cross-coupling of aziridines and allylic
chlorides in the presence of manganese metal as the reducing agent affords
β-allyl-substituted arylethylamines bearing various functional groups. The
utility of this reaction was also demonstrated by scale-up preparation and
diverse transformations, including the synthesis of Baclofen and several
bioactive molecular motifs.
S. Liu, S.-L. Wang, J. Wan, S. Peng, J.-R. Zhang, H.-J. Ding, B. Zhang, H.-L.
Ni, P. Cao, P. Hu, B.-Q. Wang, B. Chen, Org. Lett., 2023, 25,
6582-6586.
A nickel-catalyzed C-S reductive cross-coupling of alkyl halides with
arylthiosilanes provides alkyl aryl thioethers. This reaction offers exquisite
chemoselectivity, excellent tolerance of diverse functional groups, and wide
applications for late-stage modification of biologically relevant molecules.
Y.-Z. Yang, Y. Li, G.-F. Lv, D.-L. He, J.-H. Li, Org. Lett.,
2022, 24, 5116-5119.
A nickel-catalyzed decarbonylation of α-amino acid thioester provides efficient and
expedient access to α-aminosulfides with excellent chemoselectivity. This
aminomethylation of mercaptans shows good functional-group compatibility, tolerates a wide range
of electron-withdrawing and electron-donating substituents, and enables the
synthesis of α-aminosulfides even at a gram scale.
J.-Y. Zhou, R. Tian, Y.-M. Zhu, J. Org. Chem., 2021, 86,
12148-12157.
An unprecedented copper-catalyzed coupling reaction of unactivated alkyl halides
with N-dithiophthalimides efficiently provides disulfides or sulfides. This reaction can
be conducted under mild conditions using low-cost metal catalysts and exhibits
high chemical selectivity and functional group compatibility.
B. Li, B.-X. Liu, W. Rao, S.-S. Shen, D. Sheng, S.-Y. Wang, Org. Lett., 2024,
26, 3634-3639.
A C(sp3)-Si coupling of unactivated alkyl bromides with vinyl
chlorosilanes proceeds under mild conditions to provide alkylsilanes.
Functionalities such as Grignard-sensitive groups (e.g., acid, amide, alcohol,
ketone, and ester), acid-sensitive groups (e.g., ketal and THP protection),
alkyl fluoride and chloride, aryl bromide, alkyl tosylate and mesylate, silyl
ether, and amine were tolerated.
J. Duan, Y. Wang, L. Qi, P. Guo, X. Pang, X.-Z. Shu, Org. Lett., 2021, 23,
7855-7859.
Hydrosilylation of alkynes inevitably yields α- and
β-isomers of vinyltrialkoxysilanes. A cross-electrophile C(sp2)-C(sp2) coupling of
bromoalkenes yields exclusively α-vinyltrialkoxysilanes with good
functional group compatibility under mild reaction conditions.
B. Chindan, A. Syam, H. Mahendran, R. Rasappan, Org. Lett., 2023, 25,
7751-7756.
A nickel-catalyzed cross-electrophile coupling of aryl iodides with α-bromo
sulfoxides provides a diverse array of aryl benzyl sulfoxides under mild
conditions with excellent functional group tolerance. Optically enriched
sulfoxides could be coupled with aryl iodides to generate the corresponding
sulfoxides with excellent stereochemical integrity.
Q. Liu, T. Lin, Y.-e. Wang, W. Liang, L. Cao, X. Sheng, D. Xiong, J. Mao, Org. Lett., 2023, 25,
9153-9157.
Sulfides/selenides and sulfones can be obtained simultaneously using a
nickel-catalyzed reductive coupling and SN2 synergistic reaction of
allyl/benzyl bromides with thiosulfonates/selenosulfonates. The strategy offers
excellent step economy, mild reaction conditions, broad functional group
compatibility, and excellent yields.
J.-M. Cao, W.-C. Zhu, X.-Y. Liu, W. Rao, S.-S. Shen, D.-p. Sheng, S.-Y. Wang, Org. Lett., 2023, 25,
9207-9212.
A nickel-catalyzed reductive coupling between vinyl triflates and acid
fluorides provides an efficient access to various enones. The reaction avoids
the use of acyl or vinyl metallic reagents, proceeds with a broad range of acid
fluorides and cyclic vinyl triflates, and tolerates several functional groups.
F.-F. Pan, P. Guo, C.-L. Li, P. Su, X.-Z. Shu,
Org. Lett., 2019, 21, 3701-3705.
A stereoselective formal [3 + 2] cycloaddition of cyclopropyl ketones and
radical-acceptor alkenes to form polysubstituted cyclopentane derivatives is
catalyzed by a chiral Ti(salen) complex via a radical redox-relay mechanism. The
cycloaddition constructs two C-C bonds and two contiguous stereogenic centers
with generally excellent diastereo- and enantioselectivity.
W. Hao, J. H. Harenberg, X. Wu, S. N. MacMillan, S. Lin, J. Am. Chem. Soc.,
2018,
140, 3514-3517.
A simple, chemoselective Ni-catalyzed reductive cyclization/carboxylation of
unactivated alkyl halides with CO2 operates under mild conditions.
X. Wang, Y. Liu, R. Martin, J. Am. Chem. Soc., 2015,
137, 6476-6479.
A nickel-catalyzed reductive cross-coupling reaction of easily accessible
3-butenyl carbamoyl chloride with primary alkyl iodide provides chiral
α-alkylated pyrrolidinones with broad substrate scope and high enantiomeric
excess using a newly designed chiral 8-quinoline imidazoline ligand (Quinim).
X. Wu, J. Qu, Y. Chen, J. Am. Chem. Soc.,
2020, 142, 15654-15660.
A nickel-catalyzed reductive cyclization of broad range of enones affords
indanones in high enantiomeric induction. The versatility of this method is
demonstrated in several short stereoselective syntheses of medically valuable (R)-tolterodine,
(+)-indatraline, and (+)-multisianthol.
X. Qin, M. W. Y. Lee, J. S. Zhou,
Org. Lett., 2019, 21, 5990-5994.
Upon activation with manganese powder, a cobalt-catalyzed C-H bond activation
of coumarins with aryl halides or pseudohalides in the presence of carbon
monoxide provides various 3-aroylcoumarin derivatives under mild conditions.
R. Pashazadeh, S. Rajai-Daryasarei, S. Mirzaei, M. Soheilizad, S. Ansari, M.
Shabanian, Synthesis, 2019, 51,
3014-3020.