Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide,Green Chemistry

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Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
Green Chemistry ( IF 9.3 ) Pub Date : 2020-07-01 , DOI: 10.1039/d0gc01741h
Xiaolin Jiang _{1,

2,

3,

4,

5} , Zijun Huang _{1,

2,

3,

4,

5} , Mohamed Makha _{1,

2,

3,

4,

5} , Chen-Xia Du _{6,

7,

8,

9} , Dongmei Zhao _{9,

10,

11,

12} , Fang Wang _{1,

2,

3,

4,

5} , Yuehui Li _{1,

2,

3,

4,

5}

Affiliation

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.

中文翻译：

四配位硼酸酯作为胺与二氧化碳还原甲酰化的催化剂

我们报告三羟基芳基硼酸钠作为第一个坚固的四配位有机硼催化剂，用于CO _2的还原功能化。这些催化剂很容易从硼酸与金属氢氧化物的缩合反应中合成，可以有效地活化主族元素氢键。与BX ₃型硼烷，硼酸和金属-BAr ₄盐相比，在无过渡金属的条件下，三羟基芳基硼酸钠对各种胺（包括带有官能团的胺）表现出较高的还原性N-甲酰化反应性（106例）例如酯，烯烃，羟基，氰基，硝基，卤素，MeS–，醚基等。催化具有挑战性的吡啶胺的甲酰化反应的性能过高，为使用传统的甲酰化试剂提供了一种有前途的替代方法。机理研究支持将静电相互作用作为Si / B–H活化的关键，从而使碱金属硼酸盐成为用于CO ₂加氢硼化，加氢硅烷化和还原甲酰化/甲基化的通用催化剂。

更新日期：2020-08-18

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