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Nozaki-Hiama-Kishi Coupling

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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 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 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.

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.

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.