- Zinc Powder Catalysed Formylation and Urealation of Amines Using CO2 as a C1 Building Block?
-
Transformation of CO2 into valuable organic compounds catalysed by cheap and biocompatible metal catalysts is one of important topics of current organic synthesis and catalysis. Herein, we report the zinc powder catalysed formylation and urealation of amines with CO2 and (EtO)3SiH under solvent free condition. Using 2 molpercent zinc powder as the catalyst, a series of secondary amines, both the aromatic ones and the aliphatic ones, can be formylated into formamides. When primary aromatic amines were used as the substrates, the reactions produce urea derivatives. The electronic and steric effects from the substrates on the formylation and urealation reactions were observed and discussed. The recovery and reusability of zinc powder were investigated, showing the zinc powder can be reused in the formylation reaction without loss of catalytic activity. The analysis on the reactants/products mixture after filtering out the zinc powder showed the zinc concentration in the mixture is low to 1 ppm. The pathways for the formylation and urealation of amines with this catalytic system were also investigated, and related to the different substrates.
- Du, Chongyang,Chen, Yaofeng
-
p. 1057 - 1064
(2020/06/30)
-
- Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
-
We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
- Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
-
supporting information
p. 5317 - 5324
(2020/09/17)
-
- Iron-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2
-
We herein describe an efficient iron-catalyzed selective N-methylation and N-formylation of amines with CO2 and silane using mono-phosphine as ligand. With commercially available [CpFe(CO)2]2 as catalyst, Fe-catalyzed methylation of amines was achieved with triphenylphosphine as a ligand. Using tributylphosphine as a ligand, Fe-catalyzed formylation of amines was realized at a lower temperature. The method was successfully applied in the late-stage methylation and formylation of drug molecules containing amine moiety. (Figure presented.).
- Li, Wen-Duo,Zhu, Dao-Yong,Li, Gang,Chen, Jie,Xia, Ji-Bao
-
supporting information
p. 5098 - 5104
(2019/11/03)
-
- Mesoionic pyrido[1,2-a]pyrimidinones: A novel class of insecticides inhibiting nicotinic acetylcholine receptors
-
A novel class of mesoionic pyrido[1,2-a]pyrimidinones has been discovered with exceptional insecticidal activity controlling a number of insect species, particularly hemiptera and lepidoptera. Mode-of-action studies showed that they act on nicotinic acetylcholine receptors (nAChRs) primarily as inhibitors. Here we report the discovery, evolution, and preparation of this class of chemistry. Our efforts in structure–activity relationship elucidation and biological activity evaluation are also presented.
- Zhang, Wenming,Holyoke, Caleb W.,Barry, James,Leighty, Robert M.,Cordova, Daniel,Vincent, Daniel R.,Hughes, Kenneth A.,Tong, My-Hanh T.,McCann, Stephen F.,Xu, Ming,Briddell, Twyla A.,Pahutski, Thomas F.,Lahm, George P.
-
p. 5444 - 5449
(2016/11/11)
-
- Ru-catalyzed hydroamidation of alkenes and cooperative aminocarboxylation procedure with chelating formamide
-
(Matrix presented) A strategy of chelation-assisted activation of formamide was employed to achieve hydroamidation of alkenes to generate one-carbon-elongated amides in moderate to good selectivity and yields. Also reported is the two-metal-catalyzed cooperative aminocarboxylation of aryl iodides, in which Ru is presumed to catalyze decarbonylation of formamide to release carbon monoxide and amine for the subsequent Pd-catalyzed aminocarboxylation routes, thus enabling the net transformation to be performed in the absence of external CO pressure.
- Ko, Sangwon,Han, Hoon,Chang, Sukbok
-
p. 2687 - 2690
(2007/10/03)
-
- ASYMMETRIC REDUCTION OF PROCHIRAL CYCLIC KETONES WITH LITHIUM ALUMINIUM HYDRIDE PARTIALLY DECOMPOSED BY (1R,2S)-(-)-N-METHYLEPHEDRINE AND 2-ALKYLAMINOPYRIDINE
-
The title chiral hydride was found to reduce prochiral cyclic ketones, affording the corresponding optically active cyclic alcohols in high optical (max. 98percentee) yields.
- Kawasaki, Motoji,Suzuki, Yasutaka,Terashima, Shiro
-
p. 239 - 242
(2007/10/02)
-
- A ONE POT SYNTHESIS OF UNSYMMETRICAL SECONDARY ALCOHOLS FROM TWO GRIGNARD REAGENTS
-
The sequential addition of two Grignard reagents to 2-(N-methyl-N-formyl)-amino-pyridine in tetrahydrofuran provides a high yield one pot synthesis of unsymmetrical secondary alcohols.
- Comins, Daniel L.,Dernell, William
-
p. 1085 - 1088
(2007/10/02)
-
