- Sequential Organozinc Formation and Negishi Cross-Coupling of Amides Catalysed by Cobalt Salt
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Herein, a cobalt-catalysed Negishi-type cross-coupling of amide derivatives is described. Apart from being the first example of cobalt-catalysed Negishi-type coupling of amides, the process described employs a unique, simple, and cheap catalytic system to perform both the organozinc formation and the Negishi-type coupling. Indeed, the same cobalt(II) bromide salt used to form the arylzinc species from aryl bromides is then re-used to perform the cross coupling of this resulting arylzinc with N-benzoyl glutarimides at room temperature. The main advantages of the reaction presented are its robustness and ease of use. Indeed, the reactions of organozinc formation and Negishi-type coupling are performed without precautions toward water or oxygen. (Figure presented.).
- Dorval, Céline,Dubois, Elodie,Bourne-Branchu, Yann,Gosmini, Corinne,Danoun, Grégory
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supporting information
p. 1777 - 1780
(2019/02/26)
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- Generation and Cross-Coupling of Organozinc Reagents in Flow
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A versatile flow synthesis method for in situ formation of organozinc reagents and subsequent cross-coupling with aryl halides and activated carboxylic acids is reported. Formation of organozinc reagents is achieved by pumping organic halides, in the presence of ZnCl2 and LiCl, through an activated Mg-packed column under flow conditions. This method provides efficient in situ formation of aryl, primary, secondary, and tertiary alkyl organozinc reagents, which are subsequently telescoped downstream to a Negishi or decarboxylative Negishi cross-coupling reaction. The described method offers access to a variety of C-C bond formations with organozinc reagents that are otherwise commercially unavailable or difficult to prepare under traditional batch reaction conditions.
- Herath, Ananda,Molteni, Valentina,Pan, Shifeng,Loren, Jon
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supporting information
p. 7429 - 7432
(2019/01/03)
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- Cobalt-Catalyzed Oxidative Homocoupling of Arylzinc Species
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A novel procedure for the synthesis of functionalized symmetrical biaryl compounds is described. The reaction proceeds via the oxidative homocoupling of arylzinc species formed by cobalt catalysis in the presence of air or p-benzoquinone depending on the nature of the functional group.
- Bourne-Branchu, Yann,Moncomble, Aurélien,Corpet, Martin,Danoun, Gregory,Gosmini, Corinne
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p. 3352 - 3356
(2016/09/12)
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- Synthesis of Symmetrical Diaryl Ketones by Cobalt-Catalyzed Reaction of Arylzinc Reagents with Ethyl Chloroformate
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Symmetrical diaryl ketones were prepared by a cross-coupling reaction between aryl bromides and ethyl chloroformate. This new method, which uses a catalyst composed of CoBr2and a bipyridine ligand along with readily available starting materials, allows for the synthesis of a variety of symmetrical diaryl ketones in moderate to excellent yields (37–99 %) under mild conditions. This reaction, in which ethyl chloroformate acts as a surrogate of carbon monoxide in the presence of cobalt and zinc, represents an interesting alternative to previously known approaches for the synthesis of diarylmethanones.
- Rérat, Alice,Michon, Christophe,Agbossou-Niedercorn, Francine,Gosmini, Corinne
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p. 4554 - 4560
(2016/09/23)
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- α-C-Glycosides via syn Opening of 1,2-Anhydro Sugars with Organozinc Compounds in Toluene/n-Dibutyl Ether
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The diastereoselective addition of organozinc species to 1,2-anhydro sugars in toluene/n-dibutyl ether solvent is reported. Compared to the existing methods, the reaction proceeds at 0 °C, and only a slight excess of nucleophile is required to achieve good yields. Scope was assessed with different O-protected glycals along with various nucleophiles (aryl, alkynyl). This methodology was applied to the synthesis of the α-anomer of canagliflozin.
- Wagschal, Simon,Guilbaud, Johan,Rabet, Pauline,Farina, Vittorio,Lemaire, Sébastien
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p. 9328 - 9335
(2015/09/28)
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- Nickel-catalyzed enantioselective arylation of pyridinium ions: Harnessing an iminium ion activation mode
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A nickel for your thoughts.?? An enantioselective nickel-catalyzed cross-coupling between N-acylpyridinium salts and organozinc reagents is reported. The catalytic system, which is comprised of an air-stable NiII source and a chiral phosphoramidite ligand, affords 2-substituted-2,3-dihydro-4-pyridones with up to >99 % ee. Copyright
- Chau, Stephen T.,Lutz, J. Patrick,Wu, Kevin,Doyle, Abigail G.
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supporting information
p. 9153 - 9156
(2013/09/12)
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- Directed nickel-catalyzed negishi cross coupling of alkyl aziridines
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Herein we report a nickel-catalyzed C-C bond-forming reaction between simple alkyl aziridines and organozinc reagents. This method represents the first catalytic cross-coupling reaction employing a nonallylic and nonbenzylic Csp3-N bond as an electrophile. Key to its success is the use of a new N-protecting group (cinsyl or Cn) bearing an electron-deficient olefin that directs oxidative addition and facilitates reductive elimination. Studies pertinent to elucidation of the mechanism of cross coupling are also presented.
- Nielsen, Daniel K.,Huang, Chung-Yang,Doyle, Abigail G.
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supporting information
p. 13605 - 13609
(2013/09/24)
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- Cobalt-catalyzed electrophilic amination of arylzincs with N-chloroamines
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Roles reversed: An efficient cobalt-catalyzed electrophilic amination of arylzinc reagents has been achieved. A variety of functionalized arylzincs and N-chloroamines were coupled under mild conditions (see scheme). Both secondary and tertiary arylamines were obtained in moderate to excellent yields. Copyright
- Qian, Xin,Yu, Zailu,Auffrant, Audrey,Gosmini, Corinne
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supporting information
p. 6225 - 6229
(2013/07/05)
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- Cobalt-catalysed synthesis of highly substituted styrene derivatives via arylzincation of alkynes
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A new two-step procedure was developed by carbozincation of internal and terminal alkynes to synthesise highly functionalised vinylzinc bromides. Various tri and tetrasubstituted alkenes were prepared in moderate to good yields under mild reaction conditions in a stereo-selective manner. This methodology represents an interesting alternative to previously known methods. This journal is
- Corpet, Martin,Gosmini, Corinne
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supporting information
p. 11561 - 11563,3
(2012/12/12)
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- New chemical synthesis of functionalized arylzinc compounds from aromatic or thienyl bromides under mild conditions using a simple cobalt catalyst and zinc dust
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A new chemical method for the preparation of arylzinc intermediates is described in acetonitrile, on the basis of the activation of aryl bromides by low-valent cobalt species arising from the reduction of cobalt halide by zinc dust. This procedure allows for the synthesis of a variety of functionalized aryl- and thienylzinc species in good to excellent yields. The versatility and the simplicity of that original method represent an alternative to most known procedures.
- Fillon, Hyacinthe,Gosmini, Corinne,Perichon, Jacques
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p. 3867 - 3870
(2007/10/03)
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