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Nozaki-Hiama-Kishi Coupling

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 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.

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 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 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.

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 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 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.