6639-59-4Relevant academic research and scientific papers
Acid-catalyzed chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines
Guo, Luxia,Chen, Zihao,Zhu, Hongmei,Li, Minghao,Gu, Yanlong
supporting information, p. 1419 - 1422 (2020/11/12)
Chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines were described, which were established on the basis of either a C[sbnd]C bond cleavage or a rearrangement process of a reaction intermediate. These reactions proceeded in a condition-determined manner with good functional group tolerance. In the first model, 2,2-dimethoxyacetaldehyde reacted with aniline to form a new C[sbnd]N bond, in the presence of O2, via a C[sbnd]C bond cleavage reaction. However, in the second model, by performing the reaction in the absence of O2, Heyns rearrangement occurred and generated a new C[sbnd]O bond to form methyl phenylglycinate. Such condition-determined reactions not only offered the new way for value-added conversion of biomass-derived platform molecule, 2, 2-dimethoxyacetaldehyde, but also provided efficient methods for the synthesis of N-arylformamides and methyl phenylglycinates.
Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
supporting information, p. 5317 - 5324 (2020/09/17)
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.
