Nickel-catalyzed, sodium iodide-promoted reductive dimerization of alkyl halides, alkyl pseudohalides, and allylic acetates

Prinsell, Michael R.; Everson, Daniel A.; Weix, Daniel J.

doi:10.1039/c0cc01716g

Cited by 188 publications

(115 citation statements)

References 63 publications

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“…This indicates that the redox potentials of the various Ni-tpy species are important, which is in line with our observations. Elemental manganese has been used in effective Ni-catalyzed reductive dimerization of alkyl halides, tosylates, and trifluoroacetates applying a [Ni(glyme)Cl2]/4,4′,4′′-(t-Bu)3tpy catalyst system [64]. Interestingly, the addition of NaI promotes the reaction, but the reason for this is not yet clear.…”

Section: Further Ni-tpy Catalyzed C-c Cross-coupling Reactionsmentioning

confidence: 99%

Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

2018

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Abstract:In recent years, nickel has entered the stage for catalyzed C-C cross-coupling reactions, replacing expensive palladium, and in some cases enabling the use of new substrate classes. Polypyridine ligands have played an important role in this development, and the prototypical tridentate 2,2 :6 ,2 -terpyridine (tpy) stands as an excellent example of these ligands. This review summarizes research that has been devoted to exploring the mechanistic details in catalyzed C-C cross-coupling reactions using tpy-based nickel systems.

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Section: Further Ni-tpy Catalyzed C-c Cross-coupling Reactionsmentioning

confidence: 99%

Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

2018

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“…To avoid handling the air-and moisture-sensitive organomagnesium and organozinc reagents, straightforward procedures, which do not require organometallic reagents, are highly desirable and many have now been developed. [11] To the best of our knowledge, direct transition-metal-catalyzed alkyl-allyl cross-couplings using in situ generated catalytic organometallic reagents are still unknown. However, a few years ago, we reported a related Co-catalyzed coupling reaction of aryl halides with allylic acetates; [12] these reactions in the presence of an appropriate reducing reagent, gave allylaromatic compounds.…”

mentioning

confidence: 99%

Cobalt‐Catalyzed Reductive Allylation of Alkyl Halides with Allylic Acetates or Carbonates

Qian¹,

Auffrant²,

Felouat³

et al. 2011

Angew Chem Int Ed

128

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Transition-metal-catalyzed allylic alkylations, using a broad range of metal complexes, have been intensively studied because of their potential applications in the synthesis of new olefinic compounds in particular for total synthesis.[1] Soft nucleophiles are usually used in Pd-, [1] Mo-, [2] Ir-, [3] Ru-, [4] Rh-, [5] Pt-, [6] and even Fe-catalyzed [7] allylic substitutions. Ni, [8] Co, [9] and Cu [10] catalysts allow the use of hard nucleophiles such as alkylzinc or Grignard reagents, but limited functional group compatibility and/or poor regioselectivity can be observed if the system is not designed carefully. To avoid handling the air-and moisture-sensitive organomagnesium and organozinc reagents, straightforward procedures, which do not require organometallic reagents, are highly desirable and many have now been developed. [11] To the best of our knowledge, direct transition-metal-catalyzed alkyl-allyl cross-couplings using in situ generated catalytic organometallic reagents are still unknown. However, a few years ago, we reported a related Co-catalyzed coupling reaction of aryl halides with allylic acetates; [12] these reactions in the presence of an appropriate reducing reagent, gave allylaromatic compounds. Such allylic carboxylates, whilst less reactive than allyl halides, are much more environmentally friendly.Given our previous experience with the direct Cocatalyzed functionalization, including alkylation, [11c] of aryl halides [13] we were interested to take the chemistry further, and herein we report a new and general method for direct reductive cross-coupling of allylic acetates with alkyl halides using a CoBr 2 /Mn system with an acetonitrile/pyridine solvent mixture. The approach accommodates a variety of simple and functionalized alkyl halides and substituted allylic compounds and is experimentally straightforward. Indeed it uses off-theshelf reagents without any particular precautions against air and moisture. First, we investigated the use of the readily available yet poorly reactive ethyl 4-bromobutanoate with a simple allyl acetate as the electrophile. The major challenge here lies in promoting cross-coupling rather than the formation of reduction and homocoupling products.

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“…13 4,4′,4″-tri- tert -butyl-2,2′:6′,2″-terpyridine produced large amounts of alkyl dimer product (Entry 3), but the formation of these side products was minimized when 4,4′-di- tert -butyl-2,2′-bipyridine was used as a ligand (Table 1, Entries 1 and 3). As noted by Mukaiyama, reactions conducted without a ligand provided little ketone product (Entry 2).…”

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confidence: 99%

Synthesis of Functionalized Dialkyl Ketones from Carboxylic Acid Derivatives and Alkyl Halides

2012

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Unsymmetrical dialkyl ketones can be directly prepared by the nickel-catalyzed reductive coupling of carboxylic acid chlorides or (2-pyridyl)thioesters with alkyl iodides or benzylic chlorides. A wide variety of functional groups are tolerated by this process, including common nitrogen protecting groups and C-B bonds. Even hindered ketones flanked by tertiary and secondary centers can be formed. The mechanism is proposed to involve the reaction of a (L)Ni(alkyl)2 intermediate with the carboxylic acid derivative.

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Nickel-catalyzed, sodium iodide-promoted reductive dimerization of alkyl halides, alkyl pseudohalides, and allylic acetates

Abstract: The first general method for the reductive dimerization of alkyl halides, alkyl mesylates, alkyl trifluoroacetates, and allylic acetates is reported which proceeds with low catalyst loading (0.5 to 5 mol%), generally high yields (80% ave yield), and good functional-group tolerance.

Cited by 188 publications

References 63 publications

Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

Exploring Mechanisms in Ni Terpyridine Catalyzed C–C Cross-Coupling Reactions—A Review

Cobalt‐Catalyzed Reductive Allylation of Alkyl Halides with Allylic Acetates or Carbonates

Synthesis of Functionalized Dialkyl Ketones from Carboxylic Acid Derivatives and Alkyl Halides

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