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Manganese
Product Manager
Sandra Forbes
Name Reactions
Nozaki-Hiama-Kishi Coupling
Recent Literature
A highly effective nickel-catalyzed process enables the direct reductive cross-coupling of equimolar quantities of alkyl and aryl halides in the presence of manganese, demonstrating excellent yield, functional group compatibility, and operational simplicity. This transformation bypasses the generation of organomanganese intermediates, with enhanced performance observed when utilizing a dual-ligand system.
D. A. Everson, R. Shrestha, D. J. Weix, J. Am. Chem. Soc., 2010, 132, 920-921.
DOI: 10.1021/ja9093956
A straightforward nickel-catalyzed methodology facilitates the reductive deaminative arylation at unactivated sp3 carbon centers, showcasing remarkable chemoselectivity and broad substrate applicability. This approach has proven valuable for late-stage diversification of amine-containing pharmaceuticals.
R. Martin-Montero, Y. R. Yatham, H. Yin, J. Davies, R. Martin, Org. Lett., 2019, 21, 2947-2951.
DOI: 10.1021/acs.orglett.9b01016
Various aromatic halides undergo smooth cobalt-catalyzed vinylation with β-halostyrenes, maintaining complete double bond configuration integrity when triphenylphosphine is employed as the ligand. This method establishes a novel pathway for stereoselective synthesis of functionalized stilbenes.
A. Moncomble, P. Le Floch, A. Lledos, C. Gosmini, J. Org. Chem., 2012, 77, 5056-5062.
DOI: 10.1021/jo3005149
The nickel-catalyzed asymmetric reductive coupling of vinyl bromides and benzyl chlorides enables direct formation of enantioenriched products containing aryl-substituted tertiary allylic stereocenters from stable precursors. This transformation proceeds under mild conditions, circumventing the need for preformed organometallic reagents and addressing typical regioselectivity challenges in allylic arylation.
A. H. Cherney, S. E. Reisman, J. Am. Chem. Soc., 2014, 136, 14365-14366.
DOI: 10.1021/ja508067c
A ligand-directed nickel migration/arylation strategy facilitates efficient remote reductive cross-electrophile coupling. This versatile protocol utilizes readily available alkyl and aryl bromides to synthesize diverse 1,1-diarylalkanes with excellent yield and regiocontrol under mild conditions.
F. Chen, K. Chen, Y. Zhang, Y. He, Y.-M. Wang, S. Zhu, J. Am. Chem. Soc., 2017, 139, 13929-13935.
DOI: 10.1021/jacs.7b08064
The nickel-catalyzed coupling of benzyl alcohols and aryl halides, mediated by a titanium(III) reagent generated from TiCl4 (2,6-lutidine) and manganese powder, produces cross-coupled products in high yield.
T. Suga, Y. Ukaji, Org. Lett., 2018, 20, 7846-7850.
DOI: 10.1021/acs.orglett.8b03367
A practical electrophile-electrophile coupling strategy involving carboxylic acid derivatives and alkylpyridinium salts through C-N bond cleavage delivers various functionalized ketones in excellent yields. This method accommodates both acid chlorides and free carboxylic acids as acylating agents.
F. T. Pulikottil, R. Pilli, R. V. Suku, R. Rasappan, Org. Lett., 2020, 22, 2833-2837.
DOI: 10.1021/acs.orglett.0c00554
The nickel-catalyzed asymmetric reductive trifluoroalkylation of acyl chlorides enables enantioselective synthesis of α-trifluoromethylated ketones. Subsequent one-pot reduction affords β-CF3-substituted alcohols with excellent diastereocontrol, offering high yields, enantioselectivity, and functional group tolerance.
B.-B. Wu, J. Xu, K.-J. Bian, Q. Gao, X.-S. Wang, J. Am. Chem. Soc., 2022, 144, 6543-6550.
DOI: 10.1021/jacs.2c01422
A nickel-catalyzed reductive coupling of acyl chlorides with racemic secondary α-trifluoromethyl bromides generates chiral α-CF3 carbonyl compounds with excellent enantioselectivity and functional group compatibility.
J. Wu, H. Wu, X. Liu, Y. Zhang, G. Huang, C. Zhang, Org. Lett., 2022, 24, 4322-4327.
DOI: 10.1021/acs.orglett.2c01208
An isoquinox-derived nickel complex facilitates enantioselective conjugate arylation and heteroarylation of enones using aryl and heteroaryl halides. Experimental and computational studies support a 1,4-addition mechanism involving arylnickel(I) complex insertion.
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.
DOI: 10.1021/jacs.2c05678
A remote functionalization strategy enables Z-selective synthesis of silyl enol ethers from (hetero)aromatic and aliphatic ketones via nickel-catalyzed chain walking. Mechanistic studies suggest formation of a Ni(I) dimer as the catalyst resting state, which converts to [Ni(II)-H] upon reaction with alkyl bromides.
S. Guven, G. Kundu, A. Wessels, J. S. Ward, K. Rissanen, F. Schoenebeck, J. Am. Chem. Soc., 2021, 143, 8375-8380.
DOI: 10.1021/jacs.1c01797
A chiral bisoxazoline-nickel complex catalyzes stereoselective reductive arylation of ketones with high enantioselectivity, accommodating various acyclic and cyclic ketones without requiring directing groups.
S. Huang, J. S. Zhou, J. Am. Chem. Soc., 2024, 146, 11895-112900.
DOI: 10.1021/jacs.4c02818
A mild defluorinative reductive coupling of gem-difluoroalkenes with aliphatic aldehydes provides diverse β-fluorinated allylic alcohols with good yield and 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.
DOI: 10.1021/acs.orglett.3c00016
The nickel-catalyzed carboxylation of aryl and vinyl chlorides proceeds at ambient temperature and 1 atm CO2 pressure using manganese powder as the reductant, converting various substrates to corresponding carboxylic acids in good yields.
T. Fujihara, K. Nogi, T. Xu, J. Terao, Y. Tsuji, J. Am. Chem. Soc., 2012, 134, 9106-9109.
DOI: 10.1021/ja303514b
A user-friendly nickel-catalyzed protocol enables carboxylation of unactivated primary alkyl bromides and sulfonates with CO2 at atmospheric pressure, featuring mild conditions and broad scope without requiring air- or moisture-sensitive reagents.
Y. Liu, J. Cornella, R. Martin, J. Am. Chem. Soc., 2014, 136, 11212-11215.
DOI: 10.1021/ja5064586
The catalytic carboxylation of unactivated primary, secondary, and tertiary alkyl chlorides with CO2 at atmospheric pressure demonstrates excellent chemoselectivity, mild conditions, and operational simplicity.
M. Börjesson, T. Moragas, R. Martin, J. Am. Chem. Soc., 2016, 138, 7504-7507.
DOI: 10.1021/jacs.6b04088
Nickel-catalyzed carboxylation of aryl and heteroaryl fluorosulfates with CO2 provides arene carboxylic acids in excellent yields under mild conditions, with a one-pot phenol fluorosulfation/carboxylation variant also 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.
DOI: 10.1021/acs.orglett.9b00836
A nickel-catalyzed protocol enables predictable and controlled site-selective CO2 incorporation into various unsaturated hydrocarbons, utilizing water as the formal hydride source.
M. Gaydou, T. Moragas, F. Juliá-Hernández, R. Martin, J. Am. Chem. Soc., 2017, 139, 12161-12164.
DOI: 10.1021/jacs.7b07637
A nickel-catalyzed protocol enables predictable and controlled site-selective CO2 incorporation into various unsaturated hydrocarbons, utilizing water as the formal hydride source.
M. Gaydou, T. Moragas, F. Juliá-Hernández, R. Martin, J. Am. Chem. Soc., 2017, 139, 12161-12164.
DOI: 10.1021/jacs.7b07637
An unprecedented cobalt-catalyzed process achieves highly site-, diastereo-, and enantioselective formation of nucleophilic allyl-Co(II) complexes, which subsequently add to aldehydes to produce diverse enantioenriched homoallylic alcohols with remarkable scope.
L. Wang, L. Wang, M. Li, Q. Chong, F. Meng, J. Am. Chem. Soc., 2021, 143, 12755-12765.
DOI: 10.1021/jacs.1c05690
The nickel-catalyzed reductive deaminative cross-electrophile coupling between Katritzky salts and aromatic amides generates ketones under mild conditions with excellent functional group tolerance, offering potential for late-stage functionalization of complex molecules.
C.-G. Yu, Y. Matsuo, Org. Lett., 2020, 22, 950-955.
DOI: 10.1021/acs.orglett.9b04497
A domino dehydrochlorination/Mn-enabled radical-based alkyl-alkyl cross-coupling efficiently alkylates β-chloro ketones via in situ-generated α,β-unsaturated ketone intermediates.
J. Wang, Y.-B. Pang, N. Tao, R.-S. Zeng, Y. Zhao, J. Org. Chem., 2019, 84, 15315-15322.
The cobalt-catalyzed reductive carboxylation of alkenyl triflates enables synthesis of α,β-unsaturated carboxylic acids using Mn powder as reductant under 1 atm CO2 at room temperature, with nickel or cobalt catalysts facilitating carboxylation of sterically hindered aryl triflates.
K. Nogi, T. Fujihara, J. Terao, Y. Tsuji, J. Org. Chem., 2015, 80, 11618-11623.
Unsymmetric dialkyl ketones are accessible through nickel-catalyzed reductive coupling of carboxylic acid chlorides or (2-pyridyl)thioesters with alkyl iodides or benzylic chlorides, tolerating various functional groups including nitrogen protecting groups and C-B bonds.
A. C. Wotal, D. J. Weix, Org. Lett., 2012, 14, 1363-1365.
DOI: 10.1021/ol300217x
A nickel-catalyzed three-component coupling of 1,3-dienes with aldehydes and aryl bromides using manganese as reductant produces 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.
DOI: 10.1021/acs.orglett.2c01648
The copper-catalyzed Reformatsky reaction of carbonyl compounds with ethyl iodoacetate affords β-hydroxyl esters in excellent yields from inexpensive starting materials under mild conditions.
L. Ouyang, J. H. Liao, Y. P. Xia, R. S. Luo, Synlett, 2020, 31, 1418-1422.
Nickel-catalyzed asymmetric reductive coupling of acid chlorides with racemic secondary benzyl chlorides in the presence of Mn0 generates acyclic α,α-disubstituted ketones with good yields and high enantioselectivity under mild, base-free conditions.
A. H. Cherney, N. T. Kadunce, S. E. Reisman, J. Am. Chem. Soc., 2013, 135, 7442-7445.
DOI: 10.1021/ja402922w
A mild nickel-catalyzed regioselective hydrocarboxylation converts various alkynes with CO2 (1 bar) using simple alcohols as proton sources, avoiding sensitive organometallic species.
X. Wang, M. Nakajima, R. Martin, J. Am. Chem. Soc., 2015, 137, 8924-8927.
DOI: 10.1021/jacs.5b05513
The manganese-promoted sequential reaction of dichloroesters with aldehydes yields α,β-unsaturated esters with complete stereocontrol, proceeding through a proposed aldol-type reaction/elimination mechanism.
J. M. Concellón, H. Rodríquez-Solla, P. Díaz, R. Llaona, J. Org. Chem., 2007, 72, 4396-4400.
DOI: 10.1021/jo070209w
Rieke manganese promotes complete E-selective synthesis of α,β-unsaturated amides from dichloroamides and aldehydes, which can be readily 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.
DOI: 10.1021/jo701417z
Stereoselective β-elimination of 2-bromo-3-hydroxyester diastereomers using unactivated manganese and trimethylsilyl chloride yields (E)-α,β-unsaturated esters with complete diastereoselectivity.
J. M. Concellón, H. Rodríguez-Solla, V. del Amo, Synlett, 2006, 315-317.
Nickel-catalyzed asymmetric decarboxyarylation of NHP esters via reductive coupling provides diverse chiral benzylamines with excellent catalytic efficiency, enantiocontrol, and 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.
DOI: 10.1021/acs.orglett.3c02431
Active manganese promotes regioselective transformation of N-4-methoxyphenylaziridine 2-carboxamides into 2-aminoamides, which can be converted to α-amino ketones using organolithium reagents.
J. M. Concellón, H. Rodríguez-Solla, V. del Amo, P. Díaz, J. Org. Chem., 2010, 75, 2407-2410.
DOI: 10.1021/jo902708x
Nickel-catalyzed reductive carboxylation of N-substituted aziridines with CO2 at atmospheric pressure provides β-amino acids under mild conditions with excellent 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.
DOI: 10.1021/jacs.1c01916
Chromium-catalyzed asymmetric cross aza-pinacol coupling of aldehydes and N-sulfonyl imines yields β-amino alcohols with vicinal stereocenters via a radical-polar crossover mechanism.
H. Hu, Z. Wang, J. Am. Chem. Soc., 2023, 145, 20775-20781.
DOI: 10.1021/jacs.3c08493
Nickel-catalyzed reductive coupling of aziridines and allylic chlorides using manganese as reductant affords β-allyl-substituted arylethylamines, demonstrating utility in scale-up and synthesis of bioactive molecules.
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.
DOI: 10.1021/acs.orglett.3c02399
Nickel-catalyzed C-S reductive coupling of alkyl halides with arylthiosilanes provides alkyl aryl thioethers with excellent chemoselectivity and functional group tolerance, suitable for late-stage modification of bioactive molecules.
Y.-Z. Yang, Y. Li, G.-F. Lv, D.-L. He, J.-H. Li, Org. Lett., 2022, 24, 5116-5119.
DOI: 10.1021/acs.orglett.2c01954
Nickel-catalyzed decarbonylation of α-amino acid thioesters efficiently provides α-aminosulfides with excellent chemoselectivity and functional group compatibility, enabling gram-scale synthesis.
J.-Y. Zhou, R. Tian, Y.-M. Zhu, J. Org. Chem., 2021, 86, 12148-12157.
Copper-catalyzed coupling of unactivated alkyl halides with N-dithiophthalimides efficiently provides disulfides or sulfides under mild conditions with high 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.
DOI: 10.1021/acs.orglett.4c01109
C(sp3)-Si coupling of unactivated alkyl bromides with vinyl chlorosilanes proceeds under mild conditions to provide alkylsilanes, tolerating various functional groups.
J. Duan, Y. Wang, L. Qi, P. Guo, X. Pang, X.-Z. Shu, Org. Lett., 2021, 23, 7855-7859.
DOI: 10.1021/acs.orglett.1c02874
Cross-electrophile C(sp2)-C(sp2) coupling of bromoalkenes yields exclusively α-vinyltrialkoxysilanes with good functional group compatibility under mild conditions.
B. Chindan, A. Syam, H. Mahendran, R. Rasappan, Org. Lett., 2023, 25, 7751-7756.
DOI: 10.1021/acs.orglett.3c03206
Nickel-catalyzed coupling of aryl iodides with α-bromo sulfoxides provides diverse aryl benzyl sulfoxides under mild conditions with excellent functional group tolerance and 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.
DOI: 10.1021/acs.orglett.3c03619
Nickel-catalyzed reductive coupling and SN2 reaction of allyl/benzyl bromides with thiosulfonates/selenosulfonates simultaneously provides sulfides/selenides and sulfones with excellent step economy and functional group compatibility.
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.
DOI: 10.1021/acs.orglett.3c03777
Nickel-catalyzed reductive coupling of vinyl triflates and acid fluorides provides efficient access to various enones without requiring acyl or vinyl metallic reagents, tolerating multiple functional groups.
F.-F. Pan, P. Guo, C.-L. Li, P. Su, X.-Z. Shu, Org. Lett., 2019, 21, 3701-3705.
DOI: 10.1021/acs.orglett.9b01164
Chiral Ti(salen)-catalyzed stereoselective [3+2] cycloaddition of cyclopropyl ketones and radical-acceptor alkenes forms polysubstituted cyclopentanes with excellent diastereo- and enantioselectivity via a radical redox-relay mechanism.
W. Hao, J. H. Harenberg, X. Wu, S. N. MacMillan, S. Lin, J. Am. Chem. Soc., 2018, 140, 3514-3517.
DOI: 10.1021/jacs.7b13710
Nickel-catalyzed reductive cyclization/carboxylation of unactivated alkyl halides with CO2 operates under mild conditions with excellent chemoselectivity.
X. Wang, Y. Liu, R. Martin, J. Am. Chem. Soc., 2015, 137, 6476-6479.
DOI: 10.1021/jacs.5b03340
Nickel-catalyzed reductive coupling of 3-butenyl carbamoyl chloride with primary alkyl iodides using a chiral 8-quinoline imidazoline ligand provides chiral α-alkylated pyrrolidinones with broad scope and high enantiomeric excess.
X. Wu, J. Qu, Y. Chen, J. Am. Chem. Soc., 2020, 142, 15654-15660.
DOI: 10.1021/jacs.0c07126
Nickel-catalyzed reductive cyclization of enones affords indanones with high enantiomeric induction, demonstrating utility in stereoselective synthesis of pharmaceutically relevant compounds.
X. Qin, M. W. Y. Lee, J. S. Zhou, Org. Lett., 2019, 21, 5990-5994.
DOI: 10.1021/acs.orglett.9b02130
Manganese-activated cobalt-catalyzed C-H bond activation of coumarins with aryl halides/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.
Quoted from: https://www.organic-chemistry.org/chemicals/reductions/manganese.shtm
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