- Manganese-Catalyzed Anti-Markovnikov Hydroamination of Allyl Alcohols via Hydrogen-Borrowing Catalysis
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Controlling the selectivity in a hydroamination reaction is an extremely challenging yet highly desirable task for the diversification of amines. In this article, a selective formal anti-Markovnikov hydroamination of allyl alcohols is presented. It enables the versatile synthesis of valuable γ-amino alcohol building blocks. A phosphine-free Earth's abundant manganese(I) complex catalyzed the reaction under hydrogen-borrowing conditions. A vast range of aliphatic, aromatic amines, drug molecules, and natural product derivatives underwent successful hydroamination with primary and secondary allylic alcohols with excellent functional group tolerance (57 examples). The catalysis could be performed on a gram scale and has been applied for the synthesis of drug molecules. The mechanistic studies revealed the metal-ligand bifunctionality as well as hemilability of the ligand backbone as the key design principle for the success of this catalysis.
- Das, Kuhali,Sarkar, Koushik,Maji, Biplab
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p. 7060 - 7069
(2021/06/30)
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- Iron-Catalyzed Anti-Markovnikov Hydroamination and Hydroamidation of Allylic Alcohols
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Hydroamination allows for the direct access to synthetically important amines. Controlling the selectivity of the reaction with efficient, widely applicable, and economic catalysts remains challenging, however. This paper reports an iron-catalyzed formal anti-Markovnikov hydroamination and hydroamidation of allylic alcohols, which yields γ-amino and γ-amido alcohols, respectively. Homoallylic alcohol is also feasible. The catalytic system, consisting of a pincer Fe-PNP complex (1-4 mol %), a weak base, and a nonpolar solvent, features exclusive anti-Markovnikov selectivity, broad substrate scope (>70 examples), and good functional group tolerance. The reaction could be performed at gram scale and applied to the synthesis of drug molecules and heterocyclic compounds. When chiral substrates are used, the stereochemistry and enantiomeric excess are retained. Further application of the chemistry is seen in the functionalization of amino acids, natural products, and existing drugs. Mechanistic studies suggest that the reaction proceeds via two cooperating catalytic cycles, with the iron complex catalyzing a dehydrogenation/hydrogenation process while the amine substrate acts as an organocatalyst for the Michael addition step.
- Ma, Wei,Zhang, Xiaohui,Fan, Juan,Liu, Yuxuan,Tang, Weijun,Xue, Dong,Li, Chaoqun,Xiao, Jianliang,Wang, Chao
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supporting information
p. 13506 - 13515
(2019/09/09)
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- Solvent-free copper-catalyzed N-arylation of amino alcohols and diamines with aryl halides
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A simple and mild method for the coupling of aryl halides with amino alcohols and diamines is described. The reactions can be performed under ligand-free and solvent-free conditions, and generate the products in good yield.
- Yin, Huiqing,Jin, Ming,Chen, Wei,Chen, Chen,Zheng, Likang,Wei, Ping,Han, Shiqing
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supporting information; experimental part
p. 1265 - 1270
(2012/03/27)
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- Efficient copper-catalyzed N-arylations of nitrogen-containing heterocycles and aliphatic amines in water
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A simple and efficient copper-catalyzed method has been developed for N-arylations of nitrogen-containing heterocycles and aliphatic amines in water. The protocol uses (1E,2E)-oxalaldehyde dioxime (OADO) as the ligand, and water as the solvent, and shows good tolerance towards various functional groups.
- Li, Xufeng,Yang, Daoshan,Jiang, Yuyang,Fu, Hua
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experimental part
p. 1097 - 1105
(2010/08/06)
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- POLYCYCLIC COMPOUND
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Disclosed is a compound represented by the formula (I): or a pharmacologically acceptable salt thereof, which is effective as a therapeutic or prophylactic agent for a disease induced by Aβ, wherein Ar1 represents an imidazolyl group which may be substituted with a C1-6 alkyl group, or the like; Ar2 represents a phenyl group which may be substituted with a C1-6 alkoxy group, or the like; X1 represents a double bond, or the like; and Het represents a triazolyl group or the like which may be substituted with a C1-6 alkyl group or the like, or the like.
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