181705-90-8Relevant academic research and scientific papers
Ni-Catalyzed Reductive Cyanation of Aryl Halides and Phenol Derivatives via Transnitrilation
Mills, L. Reginald,Graham, Joshua M.,Patel, Purvish,Rousseaux, Sophie A. L.
supporting information, p. 19257 - 19262 (2019/12/02)
Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2-methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.
Method for asymmetrically synthesizing (S)-preclamol
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Paragraph 0021-0024, (2019/02/04)
The invention discloses a novel method for asymmetrically synthesizing (S)-preclamol. The method comprises the following steps: using racemic alpha-halogenated glutaric acid diester as a starting material to be subjected to an asymmetric Negishi cross-coupling reaction with zinc m-methoxyphenyl bromide under the catalysis of a bisoxazoline chiral ligand and metal cobalt to obtain m-methoxyphenyl-substituted glutaric acid diester, then reducing by LiAlH4 to form (S)-2-(3-methoxyphenyl) pentanediol, and finally performing to amination cyclization and desmethylation to obtain (S)-preclamol. The asymmetric Negishi cross-coupling reaction is utilized for the first time to directly construct the chiral center of (S)-preclamol, the synthesis route is short, the reaction conditions are mild, and the total yield is 51%.
A Concise Enantioselective Synthesis of (S)-Preclamol via Asymmetric Catalytic Negishi Cross-Coupling Reaction
Zhou, Yun,Liu, Chunxiao,Wang, Lifeng,Han, Leng,Hou, Shicong,Bian, Qinghua,Zhong, Jiangchun
supporting information, p. 860 - 862 (2019/04/25)
A novel, concise, and efficient enantioselective synthesis of (S)-preclamol (87% ee, 51% total yield) has been developed. The key steps of this synthetic approach included cobalt-catalyzed asymmetric catalytic cross-coupling of α-bromo ester with arylzinc and the reduction of chiral ester to diol with a tertiary carbon atom. Moreover, it was demonstrated that our enantioselective Negishi cross-coupling was a powerful tool to construct stereogenic benzylmethyl center in chiral drugs on a gram scale.
Cobalt-Catalyzed Oxidative Homocoupling of Arylzinc Species
Bourne-Branchu, Yann,Moncomble, Aurélien,Corpet, Martin,Danoun, Gregory,Gosmini, Corinne
, p. 3352 - 3356 (2016/09/12)
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.
Nickel-catalyzed enantioselective arylation of pyridinium ions: Harnessing an iminium ion activation mode
Chau, Stephen T.,Lutz, J. Patrick,Wu, Kevin,Doyle, Abigail G.
supporting information, p. 9153 - 9156 (2013/09/12)
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
Directed nickel-catalyzed negishi cross coupling of alkyl aziridines
Nielsen, Daniel K.,Huang, Chung-Yang,Doyle, Abigail G.
supporting information, p. 13605 - 13609 (2013/09/24)
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.
PROCESS FOR THE PREPARATION OF ORGANOZINC HALIDES
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Page/Page column 5, (2013/05/09)
The present invention relates to a process for the preparation of organozinc halides with low residual alkyl or aryl halide content.
Cobalt-catalyzed electrophilic amination of arylzincs with N-chloroamines
Qian, Xin,Yu, Zailu,Auffrant, Audrey,Gosmini, Corinne
supporting information, p. 6225 - 6229 (2013/07/05)
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
New chemical synthesis of functionalized arylzinc compounds from aromatic or thienyl bromides under mild conditions using a simple cobalt catalyst and zinc dust
Fillon, Hyacinthe,Gosmini, Corinne,Perichon, Jacques
, p. 3867 - 3870 (2007/10/03)
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.
