Hydrocarbamoylation of Unsaturated Bonds by Nickel/Lewis-Acid Catalysis

Nakao, Yoshiaki; Idei, Hiroaki; Kanyiva, Kyalo Stephen; Hiyama, Tamejiro

doi:10.1021/ja901153s

Cited by 172 publications

(73 citation statements)

References 24 publications

(16 reference statements)

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“…It is a concerted reaction that combines an unsaturated ligand with an adjacent metal-ligand bond to form a product containing a new ligand with the unsaturated group formally inserted into the original covalent metalligand bond (Scheme 1). A variety of unsaturated ligands undergo migratory insertion, including carbon monoxide, carbon dioxide, alkenes, alkynes, ketones, aldehydes, and imines, and migratory insertion is a common step in numerous catalytic reactions, including hydroformylation, [1,2] hydrogenation, [3][4][5] polymerization, [6][7][8][9] hydroarylation, [10][11][12][13][14] difunctionalization of alkenes, [15][16][17][18] and the olefination of aryl halides (commonly termed the Mizoroki-Heck reaction). [19][20][21][22] In most cases, the unsaturated ligand inserts into a metalcarbon (M À C) or metal-hydrogen (M À H) bond.…”

Section: Introductionmentioning

confidence: 99%

Iridium-Catalyzed, Intermolecular Hydroetherification of Unactivated Aliphatic Alkenes with Phenols

Sevov

Hartwig

2013

J. Am. Chem. Soc.

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Metal-catalyzed addition of an O−H bond to an alkene is a desirable process because it allows for rapid access to ethers from abundant starting materials without the formation of waste, without rearrangements, and with the possibility to control the stereoselectivity. We report the intermolecular, metal-catalyzed addition of phenols to unactivated α-olefins. Mechanistic studies of this rare catalytic reaction revealed a dynamic mixture of resting states that undergo O−H bond oxidative addition and subsequent olefin insertion to form ether products.

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Section: Introductionmentioning

confidence: 99%

Iridium-Catalyzed, Intermolecular Hydroetherification of Unactivated Aliphatic Alkenes with Phenols

Sevov

Hartwig

2013

J. Am. Chem. Soc.

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“…As for alkynes, Takemoto and coworkers reported an intramolecular reaction with a Rh catalyst (Scheme 17(c)) 30) . In 2009, intermolecular addition to alkynes was first reported by Nakao, Hiyama and co-workers in the presence of a Ni(0) catalyst comb i n e d w i t h s t r o n g L ew i s a c i d s s u c h a s A l M e3 (Scheme 17(d)) 31) . Notably, the reaction proceeded under very mild conditions .…”

Section: Transformation With Formamides: Overviewmentioning

confidence: 95%

Transition-metal Catalyzed Synthesis of Carbonyl Compounds Using Formates or Formamides as Carbonyl Sources

Fujihara

Tsuji

2018

J. Jpn. Petrol. Inst.

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Various available approaches for catalytic carbonylation reactions using formates and formamides with transition metal catalysts are reviewed. Pd complexes catalyze the hydroesterification or hydrocarbamoylation of alkynes using aryl formates or formamides, respectively, as the carbonyl sources. The esterification of aryl halides with aryl formates proceeds in the presence of a Pd catalyst with suitable ligands. Using a Cu complex with a bulky bidentate phosphine ligand is used as a catalyst, boraformylation and silaformylation of allenes efficiently proceeds using alkyl formates as a formyl source.

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“…whereas we 5 and others 6 have recently developed the reaction across alkynes, 5,6 1,3-dienes, 5 and norbornene 6b catalyzed by such transition metals as nickel, 7 palladium, and rhodium. The ruthenium-catalyzed reactions across alkenes, however, require either harsh reaction conditions, 4a,4b high-pressure carbon monoxide, 4a or a pyridyl group as a directing group.…”

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confidence: 95%

“…Bulky phosphorus ligands such as P(i-Pr) 3 and P(t-Bu) 3 , which were effective for the intramolecular hydrocarbamoylation of alkenes, 5 gave the corresponding linear alkanamide 3aa exclusively albeit in low yield (Entries 1 and 2). Encouraged by the observed excellent regioselectivity, which was never achieved with the reported ruthenium catalysis with such simple aliphatic 1-alkenes as 2a, we further explored other ligands to improve the yield of 3aa and found that NHC ligands were highly effective (Entries 36).…”

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confidence: 99%

Regioselective Hydrocarbamoylation of 1-Alkenes

et al. 2012

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Nickel/Lewis acid cooperative catalysis derived from [Ni(cod) 2 ], AlEt 3 , and N-heterocyclic carbene (NHC) effects highly regioselective hydrocarbamoylation of 1-alkenes. Variously substituted formamides and 1-alkenes can be employed to give a range of linear alkanamides regioselectively.Preparation of amides under neutral conditions without the need for toxic reagents and chemical wastes is still challenging in synthetic organic chemistry, 1 although a number of methods for the synthesis of amides are available.2 Aminocarbonylation of unsaturated CC bonds would offer an alternative and wastefree access to amides. In addition, regioselectivity of these ruthenium-catalyzed reactions is reportedly modest particularly with simple aliphatic 1-alkenes such as 1-hexene, giving linear alkanamides contaminated with a significant amount of branched amides as a minor component. 4 The regioselective hydrocarbamoylation of alkenes can be achieved via a radical pathway. 8 However, the addition reaction competes with alkylation of N-substituents. The hydrocarbamoylation of 1-alkenes with high linear selectivity and broad scope of substrates is highly desired as a novel transformation potentially applicable to industrial production of bulk chemicals without use of toxic carbon monoxide. Given the importance of such "anti-Markovnikov" functionalization of 1-alkenes, 9 we report herein that nickel/Lewis acid catalysis effects exclusively linear selective hydrocarbamoylation of 1-alkenes.Our initial attempt to establish the regioselective hydrocarbamoylation was commenced with the reaction of DMF (1a) with 1-tridecene (2a) in the presence of [Ni(cod) 2 ] (5 mol %) various ligands, and 20 mol % of AlMe 3 as a cocatalayst in toluene at 130°C (Table 1). Bulky phosphorus ligands such as P(i-Pr) 3 and P(t-Bu) 3 , which were effective for the intramolecular hydrocarbamoylation of alkenes, 5 gave the corresponding linear alkanamide 3aa exclusively albeit in low yield (Entries 1 and 2). Encouraged by the observed excellent regioselectivity, which was never achieved with the reported ruthenium catalysis with such simple aliphatic 1-alkenes as 2a, we further explored other ligands to improve the yield of 3aa and found that NHC ligands were highly effective (Entries 36). Particularly, IAd was found optimum to give 3aa in 62% yield after 2 h (Entry 6).With IAd as a ligand, we next examined solvents for the reaction (Entries 711). Generally, nonpolar solvents were found to give yields of 3aa better than with polar solvents, and, thus, the use of 1a as a solvent was not effective (Entry 11). At this stage, we noted the formation of a significant amount of insoluble precipitates, which were tentatively ascribed to decomposition of either of the metal catalysts. Because this could cause the observed modest yields of 3aa, we simply lowered the reaction temperature to 100°C to find that the formation of the precipitates was slowed and the yield of 3aa was improved (Entry 12). Whereas the reaction run at lower temperature slowed the reaction, ...

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Hydrocarbamoylation of Unsaturated Bonds by Nickel/Lewis-Acid Catalysis

Cited by 172 publications

References 24 publications

Iridium-Catalyzed, Intermolecular Hydroetherification of Unactivated Aliphatic Alkenes with Phenols

Iridium-Catalyzed, Intermolecular Hydroetherification of Unactivated Aliphatic Alkenes with Phenols

Transition-metal Catalyzed Synthesis of Carbonyl Compounds Using Formates or Formamides as Carbonyl Sources

Regioselective Hydrocarbamoylation of 1-Alkenes

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