Nickel‐Catalyzed Kumada Reaction of Tosylalkanes with Grignard Reagents to Produce Alkenes and Modified Arylketones

Wu, Jun; Gong, Lei; Xia, Yuanzhi; Song, Ren‐Jie; Xie, Yu; Li, Jin‐Heng

doi:10.1002/anie.201205969

Cited by 68 publications

(25 citation statements)

References 60 publications

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“…Allylic substitution with Grignard reagents was also enabled by copper [90] or iron [91] catalysis (Scheme 42a, b). Benzylic sulfones and α-sulfonylacetophenones can be alkylated under nickel catalysis (Scheme 42c) [92].…”

Section: Scheme 41 Alkylation Of Alkenyl Sulfones Under Nickel or Iromentioning

confidence: 99%

C–S Bond Activation

2018

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Section: Scheme 41 Alkylation Of Alkenyl Sulfones Under Nickel or Iromentioning

confidence: 99%

C–S Bond Activation

2018

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“…5). 39 Although not discussed by the authors, the coupling of the α-keto sulfones is likely proceeding by initial enolization of the substrate by the basic Grignard reagent (p K a PhCOCH 2 SO 2 Ph = 11.4 in DMSO 40 ), so that the β-oxido vinyl sulfone is the active electrophile; this would also account for the lack of Grignard reagent addition to the keto group.…”

Section: Introductionmentioning

confidence: 99%

Iron-Catalyzed Cross-Coupling of Unactivated Secondary Alkyl Thio Ethers and Sulfones with Aryl Grignard Reagents

2013

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The first systematic investigation of unactivated aliphatic sulfur compounds as electrophiles in transition metal-catalyzed cross-coupling are described. Initial studies focused on discerning the structural and electronic features of the organosulfur substrate which enable the challenging oxidative addition to the C(sp3)–S bond. Through extensive optimization efforts, an Fe(acac)3-catalyzed cross-coupling of unactivated alkyl aryl thio ethers with aryl Grignard reagents was realized, in which a nitrogen “directing group” on the S-aryl moiety of the thio ether served a critical role in facilitating the oxidative addition step. In addition, alkyl phenyl sulfones were found to be effective electrophiles in the Fe(acac)3-catalyzed cross-coupling with aryl Grignard reagents. For the latter class of electrophile, a thorough assessment of the various reaction parameters revealed a dramatic enhancement in reaction efficiency with an excess of TMEDA (8.0 equiv). The optimized reaction protocol was used to evaluate the scope of the method with respect to both the organomagnesium nucleophile and sulfone electrophile.

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“…The literature is replete with examples of sulfones serving a variety of different roles in synthesis, from facilitating olefin formation and cycloadditions to their use in two-electron cross-couplings. In the latter regard, the independent work of the Crudden (13) and Li (14) research groups has stood out for their use of benzylic phenyl sulfones in a variety of Pd- and nickel (Ni)–catalyzed desulfonylative cross-coupling methodologies. The first systematic study of the use of an unactivated alkyl sulfone for RCC emerged in 2013 from the Denmark laboratory’s report of iron (Fe)–catalyzed Kumada cross-coupling to forge C(sp 2 )–C(sp 3 ) bonds (15).…”

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Modular radical cross-coupling with sulfones enables access to sp ³ -rich (fluoro)alkylated scaffolds

Merchant

Edwards

Qin

et al. 2018

Science

191

119

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Cross-coupling chemistry is widely applied to carbon-carbon bond formation in the synthesis of medicines, agrochemicals, and other functional materials. Recently, single-electron-induced variants of this reaction class have proven particularly useful in the formation of C(sp)-C(sp) linkages, although certain compound classes have remained a challenge. Here, we report the use of sulfones to activate the alkyl coupling partner in nickel-catalyzed radical cross-coupling with aryl zinc reagents. This method's tolerance of fluoroalkyl substituents proved particularly advantageous for the streamlined preparation of pharmaceutically oriented fluorinated scaffolds that previously required multiple steps, toxic reagents, and nonmodular retrosynthetic blueprints. Five specific sulfone reagents facilitate the rapid assembly of a vast set of compounds, many of which contain challenging fluorination patterns.

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Nickel‐Catalyzed Kumada Reaction of Tosylalkanes with Grignard Reagents to Produce Alkenes and Modified Arylketones

Cited by 68 publications

References 60 publications

C–S Bond Activation

C–S Bond Activation

Iron-Catalyzed Cross-Coupling of Unactivated Secondary Alkyl Thio Ethers and Sulfones with Aryl Grignard Reagents

Modular radical cross-coupling with sulfones enables access to sp ³ -rich (fluoro)alkylated scaffolds

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Nickel‐Catalyzed Kumada Reaction of Tosylalkanes with Grignard Reagents to Produce Alkenes and Modified Arylketones

Cited by 68 publications

References 60 publications

C–S Bond Activation

C–S Bond Activation

Iron-Catalyzed Cross-Coupling of Unactivated Secondary Alkyl Thio Ethers and Sulfones with Aryl Grignard Reagents

Modular radical cross-coupling with sulfones enables access to sp 3 -rich (fluoro)alkylated scaffolds

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Modular radical cross-coupling with sulfones enables access to sp ³ -rich (fluoro)alkylated scaffolds