Endergonic addition of <i>N</i>-methylamines to aromatic ketones driven by photochemical offset of the entropic cost
作者:Takahiro Iwamoto、Atsushi Hosokawa、Masaharu Nakamura
DOI:10.1039/c9cc06011a
日期:——
The reaction represents an obvious example showing that the photochemical approach is effective to offset such an entropic cost, and thereby to drive thermodynamically uphill addition reactions. Moreover the present reactions are highly expedient from the synthetic view point, being transition-metal-catalyst-free, scalable, highly atom economical, and regioselective. The product amines can be converted
分子间加成反应通常由于反应过程中分子数目的减少而伴随着熵的损失,这有时使反应呈负电荷。在这里,我们证明了可以用光能作为驱动力来促进这种电子反应。ñ将-甲胺加到芳族酮中,在紫外光照射下产生氨基醇。该反应代表了一个明显的例子,表明光化学方法可有效抵消这种熵成本,从而推动热力学上的加成反应。此外,从合成的观点来看,本反应是高度方便的,是无过渡金属催化剂,可扩展的,高度原子经济的和区域选择性的。产物胺可以一步转化为功能性多芳基化烯胺,这在电子材料中可能是有价值的化合物。