13395-54-5Relevant articles and documents
Capture of Reactive Monophosphine-Ligated Palladium(0) Intermediates by Mass Spectrometry
Zheng, Qiuling,Liu, Yong,Chen, Qinghao,Hu, Meihong,Helmy, Roy,Sherer, Edward C.,Welch, Christopher J.,Chen, Hao
, p. 14035 - 14038 (2015)
A long-sought-after reactive monophosphine-ligated palladium(0) intermediate, Pd0L (L = phosphine ligand), was detected for the first time from the activation of the Buchwald precatalyst with base. The detection was enabled using desorption electrospray ionization mass spectrometry (DESI-MS) in combination with online reaction monitoring. The subsequent oxidative addition of Pd0L with aryl halide and C-N coupling with amine via reductive elimination was also probed using DESI-MS.
BF3·Et2O as a metal-free catalyst for direct reductive amination of aldehydes with amines using formic acid as a reductant
Fan, Qing-Hua,Liu, Xintong,Luo, Zhenli,Pan, Yixiao,Xu, Lijin,Yang, Ji,Yao, Zhen,Zhang, Xin
supporting information, p. 5205 - 5211 (2021/07/29)
A versatile metal- and base-free direct reductive amination of aldehydes with amines using formic acid as a reductant under the catalysis of inexpensive BF3·Et2O has been developed. A wide range of primary and secondary amines and diversely substituted aldehydes are compatible with this transformation, allowing facile access to various secondary and tertiary amines in high yields with wide functional group tolerance. Moreover, the method is convenient for the late-stage functionalization of bioactive compounds and preparation of commercialized drug molecules and biologically relevant N-heterocycles. The procedure has the advantages of simple operation and workup and easy scale-up, and does not require dry conditions, an inert atmosphere or a water scavenger. Mechanistic studies reveal the involvement of imine activation by BF3and hydride transfer from formic acid.
Combined KOH/BEt3Catalyst for Selective Deaminative Hydroboration of Aromatic Carboxamides for Construction of Luminophores
Li, Jinshan,Wang, Jiali,Yang, Jianguo,Yao, Wubing,Zhong, Aiguo
supporting information, p. 8086 - 8090 (2020/11/03)
The selective catalytic C-N bond cleavage of amides into value-added amine products is a desirable but challenging transformation. Molecules containing iminodibenzyl motifs are prevalent in pharmaceutical molecules and functional materials. Here we established a combined KOH/BEt3 catalyst for deaminative hydroboration of acyl-iminodibenzyl derivatives, including nonheterocyclic carboxamides, to the corresponding amines. This novel transition-metal-free methodology was also applied to the construction of Clomipramine and luminophores.
Sodium Triethylborohydride-Catalyzed Controlled Reduction of Unactivated Amides to Secondary or Tertiary Amines
Yao, Wubing,He, Lili,Han, Deman,Zhong, Aiguo
, (2019/11/14)
The first transition-metal-free catalytic protocol for controlled reduction of amide functions using cheap and bench-stable hydrosilanes as reducing agents has been established. By altering the hydrosilane and solvent, the new method enables the selective cleavage of unactivated C-O bonds in amides and allows the C-N bonds to selectively break via the deacylated cleavage. Overall, this novel process may offer a versatile alternative to current methodologies employing stoichiometric metal systems for the controlled reduction of carboxamides.
Sodium Triethylborohydride-Catalyzed Controlled Reduction of Unactivated Amides to Secondary or Tertiary Amines
Yao, Wubing,He, Lili,Han, Deman,Zhong, Aiguo
, p. 14627 - 14635 (2019/12/02)
The first transition-metal-free catalytic protocol for controlled reduction of amide functions using cheap and bench-stable hydrosilanes as reducing agents has been established. By altering the hydrosilane and solvent, the new method enables the selective cleavage of unactivated C-O bonds in amides and allows the C-N bonds to selectively break via the deacylated cleavage. Overall, this novel process may offer a versatile alternative to current methodologies employing stoichiometric metal systems for the controlled reduction of carboxamides.
Method for selective reducing reaction of tertiary aryl amide and borane
-
Paragraph 0061-0064, (2019/10/23)
The present invention relates to a method for a selective reducing reaction of a tertiary aryl amide and borane. A tertiary amine product is prepared by the reducing reaction of a tertiary aryl amidederivative and a cheap and easily available organoboron reagent under mild conditions under the convenient catalysis of a non-transition metal compound sodium triethylborohydride used as a catalyst for the first time. Compared with traditional methods, the method of the method generally has the advantages of wide universality of a substrate, low cost and easy availability of the catalyst, and simplicity in reaction operation. The selective reducing reaction of the tertiary aryl amide compound and the organoboron reagent under the catalysis of the transition metal catalyst is realized for the first time, and a brand new "green" reaction strategy is provided for the laboratory preparation or industrial production of tertiary arylamine products.
Tailored Cobalt-Catalysts for Reductive Alkylation of Anilines with Carboxylic Acids under Mild Conditions
Liu, Weiping,Sahoo, Basudev,Spannenberg, Anke,Junge, Kathrin,Beller, Matthias
supporting information, p. 11673 - 11677 (2018/09/10)
The first cobalt-catalyzed hydrogenative N-methylation and alkylation of amines with readily available carboxylic acid feedstocks as alkylating agents and H2 as ideal reductant is described. Combination of tailor-made triphos ligands with cobalt(II) tetrafluoroborate significantly improved the efficiency, thus promoting the reaction under milder conditions. This novel protocol allows for a broad substrate scope with good functional group tolerance, even in the presence of reducible alkenes, esters, and amides.
Novel nonmetal catalytic bidirectional selective reduction method of tertiary aromatic amide
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Paragraph 0074; 0075; 0076; 0077, (2017/10/22)
The invention relates to a novel effective bidirectional selective environment-friendly method for hydrosilation reduction of tertiary aromatic amide and an organic silicon reagent. The method comprises the following steps: selecting a nonmetal catalytic system, and selectively preparing a secondary or tertiary organic amine compound by successively catalyzing tertiary aromatic amide and cheap PHMS or triethoxysilane under a mild condition. By adopting the method, the bidirectional selective reduction of the tertiary aromatic amide is realized by innovatively utilizing an electronic effect and steric hindrance difference of an organic silicon reagent at first time, so that a brand new strategy is provided for the reduction of amide and derivative of the amide, the defects of the traditional method that the substrate functional group is poor in compatibility, the production cost is high and the like can be overcome, and the application prospect of the amine compound prepared in industrial production or laboratory is promising.
Deoxygenation of tertiary amine N-oxides under metal free condition using phenylboronic acid
Gupta, Surabhi,Sureshbabu, Popuri,Singh, Adesh Kumar,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
supporting information, p. 909 - 913 (2017/02/15)
A simple and efficient method for the deoxygenation of amine N-oxides to corresponding amines is reported using the green and economical reagent phenylboronic acid. Deoxygenation of N,N-dialkylaniline N-oxides, trialkylamine N-oxides and pyridine N-oxides were achieved in good to excellent yields. The reduction susceptible functional groups such as ketone, amide, ester and nitro groups are well tolerated with phenylboronic acid during the deoxygenation process even at high temperature. In addition, an indirect method for identification and quantification of tert-amine N-oxide is demonstrated using UV–Vis spectrometry which may be useful for drug metabolism studies.
Esters, Including Triglycerides, and Hydrogen as Feedstocks for the Ruthenium-Catalyzed Direct N-Alkylation of Amines
Adam, Rosa,Cabrero-Antonino, Jose R.,Junge, Kathrin,Jackstell, Ralf,Beller, Matthias
supporting information, p. 11049 - 11053 (2016/10/13)
Triglycerides are used for the direct N-alkylation of amines with molecular hydrogen for the first time. A broad range of interesting and industrially relevant secondary and tertiary amines are obtained in the presence of an in situ formed Ru/Triphos complex. Notably, plant oil can be efficiently applied in this single-step process. Moreover, a variety of other methyl esters can be used as N-alkylation agents in the presence of hydrogen for the synthesis of more advanced building blocks.
