Iron-Catalyzed Grignard Cross-Couplings with Allylic Methyl Ethers or Allylic Trimethylsilyl Ethers

Chika Seto; Takeshi Otsuka; Yoshiki Takeuchi; Daichi Tabuchi; Takashi Nagano

doi:10.1055/s-0036-1591774

Iron-Catalyzed Grignard Cross-Couplings with Allylic Methyl Ethers or Allylic Trimethylsilyl Ethers

Synlett ◽

10.1055/s-0036-1591774 ◽

2018 ◽

Vol 29 (09) ◽

pp. 1211-1214 ◽

Cited By ~ 1

Author(s):

Chika Seto ◽

Takeshi Otsuka ◽

Yoshiki Takeuchi ◽

Daichi Tabuchi ◽

Takashi Nagano

Keyword(s):

Cross Coupling ◽

Grignard Reagents ◽

Allylic Substitution ◽

Trimethylsilyl Ethers

We have found that cross-coupling between aryl Grignard reagents and allylic methyl ethers proceeded well in the presence of a catalytic amounts of Fe(acac)3 to afford the corresponding allylic substitution products in good yields. Under the same conditions, allylic trimethylsilyl ethers also reacted with Grignard reagents to give the corresponding cross-coupling products.

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Fe-Catalyzed Conjunctive Cross-Couplings of Unactivated Alkenes with Grignard Reagents

10.26434/chemrxiv.12049377.v1 ◽

2020 ◽

Author(s):

Lei Liu ◽

Wes Lee ◽

Cassandra R. Youshaw ◽

Mingbin Yuan ◽

Michael B. Geherty ◽

...

Keyword(s):

Functional Groups ◽

Cross Coupling ◽

Alkyl Halides ◽

Grignard Reagents ◽

Turnover Frequency ◽

Diverse Range ◽

Cascade Cyclization ◽

Radical Cascade

The first iron-catalyzed three-component cross-coupling of unactivated olefins with alkyl halides and Grignard reagents is reported. The reaction operates under fast turnover frequency and tolerates a diverse range of sp2-hybridized nucleophiles, alkyl halides, and unactivated olefins bearing diverse functional groups to yield the desired 1,2-alkylarylated products with high regiocontrol. Further, we demonstrate that this protocol is amenable for the synthesis of new (hetero)carbocycles including tetrahydrofurans and pyrrolidines via a three-component radical cascade cyclization/arylation that forges three new C-C bonds.

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Design and Development of Fe-Catalyzed Intra- and Intermolecular Carbofunctionalization of Vinyl Cyclopropanes

10.26434/chemrxiv.9858500.v1 ◽

2019 ◽

Cited By ~ 1

Author(s):

Lei Liu ◽

Wes Lee ◽

Mingbin Yuan ◽

Chris Acha ◽

Michael B. Geherty ◽

...

Keyword(s):

Bond Formation ◽

Cross Coupling ◽

Alkyl Halides ◽

Grignard Reagents ◽

Mechanistic Studies ◽

Radical Intermediates ◽

Design And Implementation ◽

Solvent Cage ◽

Radical Cascade ◽

Radical Processes

Design and implementation of the first (asymmetric) Fe-catalyzed intra- and intermolecular difunctionalization of vinyl cyclopropanes (VCPs) with alkyl halides and aryl Grignard reagents has been realized via a mechanistically driven approach. Mechanistic studies support the diffusion of the alkyl radical intermediates out of the solvent cage to participate in an intra- or -intermolecular radical cascade with the VCP followed by re-entering the Fe radical cross-coupling cycle to undergo selective C(sp2)-C(sp3) bond formation. Overall, we provide new design principles for Fe-mediated radical processes and underscore the potential of using combined computations and experiments to accelerate the development of challenging transformations.

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