- Betaine Catalysis for Hierarchical Reduction of CO2 with Amines and Hydrosilane To Form Formamides, Aminals, and Methylamines
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An efficient, sustainable organocatalyst, glycine betaine, was developed for the reductive functionalization of CO2 with amines and diphenylsilane. Methylamines and formamides were obtained in high yield by tuning the CO2 pressure and reaction temperature. Based on identification of the key intermediate, that is, the aminal, an alternative mechanism for methylation involving the C0 silyl acetal and aminal is proposed. Furthermore, reducing the CO2 amount afforded aminals with high yield and selectivity. Therefore, betaine catalysis affords products with a diversified energy content that is, formamides, aminals and methylamines, by hierarchical two-, four- and six-electron reduction, respectively, of CO2 coupled with C?N bond formation.
- Liu, Xiao-Fang,Li, Xiao-Ya,Qiao, Chang,Fu, Hong-Chen,He, Liang-Nian
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supporting information
p. 7425 - 7429
(2017/06/13)
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- Bridging amines with CO2: Organocatalyzed reduction of CO2 to aminals
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The four-electron reduction of CO2 in the presence of secondary aromatic amines is described for the first time to access aminals. Under metal-free hydrosilylation conditions, the four C-O bonds of CO2 are cleaved, and the organocatalysts are able to balance the reactivity of CO2 to promote the selective formation of two C-N and two C-H bonds. The methodology enables the formation of various symmetrical and unsymmetrical aminals.
- Frogneux, Xavier,Blondiaux, Enguerrand,Thuéry, Pierre,Cantat, Thibault
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p. 3983 - 3987
(2015/11/11)
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- Phosphorus-Nitrogen Compounds. Part 49. The Synthesis and Mechanism of Formation of 6-Chloro-5,6,7,12-tetrahydro-2,5,7,10-tetramethyldibenzo-diazaphosphocine 6-Oxide and 6-Sulphide
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A reaction mechanism is proposed for the formation of the title compounds in the reactions between N,N-dimethyl-p-toluidine and phosphoryl and thiophosphoryl chlorides.The synthesis of 2,2'-methylenebis(p-toluidine) and 2,2'-methylenebis(N-methyl-p-toluidine) are described, as are their reactions with phosphoryl and thiophosphoryl chlorides.
- Demir, Tuersen,Shaw, Robert A.
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p. 1547 - 1552
(2007/10/02)
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- Aromatic Amines and their Derivatives. Part 3. The Synthesis and Crystal Structure of 4,4'-NN'-Tetramethyl-NN'-dinitroso-2,2'-methylenedianiline
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The synthesis of 4,4',NN'-tetramethyl-NN'-dinitroso-2,2'-methylenedianiline (1) by the route p-MeC6H4NH2 + HCHO + OH- ---> (p-MeC6H4NMe)2CH2 (7b); (7b) + acid at 70 deg C ---> 4,N-dimethyl-6-(N-methyl-p-toluidinomethyl)aniline (4b); (4b) + acid at 130 deg
- Chakrabarti, Pinakpani,Venkatesan, Kailasam,Cameron, Theodore Stanley,Demir, Tuersen,Shaw, Robert A.
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p. 206 - 211
(2007/10/02)
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