2026年2月24日

化学家原以为磷元素已尽显其能——直到它展现出令人惊喜的新本领

Chemists thought phosphorus had shown all its cards—until it surprised them with a new move

作者：霍莉·奥伯（Holly Ober），加州大学洛杉矶分校

编辑：萨迪·哈雷（Sadie Harley），审校：罗伯特·伊根（Robert Egan）

by Holly Ober, University of California, Los Angeles

edited by Sadie Harley, reviewed by Robert Egan

光照射下的光化学反应

Photochemical reaction under light irradiation

加州大学洛杉矶分校的有机化学家取得了一项可能让催化转化器盗贼失业的发现。在新研究中，他们使用储量丰富、价格低廉的磷作为催化剂，完成了通常需要铂等贵金属才能实现的化学反应——而铂正是汽车催化转化器中被盗目标金属之一，这种汽车部件能将尾气中的化学物质转化为危害较小的形态。

A discovery by UCLA organic chemists may one day put catalytic converter thieves out of business. In new research, they've used abundant, inexpensive phosphorus as a catalyst in chemical reactions that usually require precious metals like platinum, one of the metals targeted in theft of the automotive components that convert chemicals in vehicle exhaust into less harmful forms.

然而，这一进展可能对制药业更为有用，并有望在未来降低某些药品的价格。

This advance, however, will likely be more useful in the pharmaceutical industry and could one day help bring down the price of some drugs.

基于磷的催化新方法

New phosphorus-based approach to catalysis

这项发表在《自然》杂志上的新研究使用了一种光反应分子（即光催化剂），该分子与廉价的含磷化合物反应，将含氮化合物（常见于药物中）与碳碳双键偶联。这种称为氢胺化的反应是构建更复杂结构的有效方法。

The new research, published in Nature, uses a light-reactive molecule, known as a photocatalyst, that reacts with an inexpensive phosphorous compound to couple nitrogen-containing compounds (often found in drugs) to a carbon-carbon double bond. This type of reaction, called hydroamination, is an effective way to make more complex structures.

"碳氮键是药物发现和制造中最重要的化学键之一。几乎所有药物都含有氮，但将氮固定到分子中很困难，这就是我们使用贵金属过渡金属催化剂的原因，"该论文的通讯作者、加州大学洛杉矶分校化学教授阿比盖尔· Doyle（Abigail Doyle）表示。

"Carbon-nitrogen bonds are some of the most important kinds of bonds for drug discovery and manufacturing. Almost all medicines have nitrogen in them, but fixing that nitrogen into molecules is difficult, which is why we use precious transition metal catalysts," said UCLA chemistry professor Abigail Doyle, who is the paper's corresponding author.

过渡金属是闪亮、导电的金属，如金、银、铜、铱、铂和钯。在适当条件下，它们容易与许多其他元素反应，加速化学反应。因此，它们已成为必不可少的工业催化剂。

Transition metals are shiny, electrically conductive metals such as gold, silver, copper, iridium, platinum and palladium. Under the right conditions, they react easily with many other elements, speeding up chemical reactions. They have therefore become essential industrial catalysts.

"这些金属用于汽车发动机的催化转化器，以及制造各种材料，从牛仔裤的组成部分到药品，"Doyle说。

"These metals are used in catalytic converters in car engines, and to make a vast variety of materials, from components of denim jeans to medicines," said Doyle.

"然而，使用它们可能非常昂贵，因此人们非常感兴趣寻找更便宜的过渡金属来替代，如铜、镍或铁，或者寻找周期表中其他既储量丰富又能像金属一样反应的催化剂。"

"However, they can be very expensive to use, so there's a lot of interest in either finding less expensive transition metals to replace these, such as copper, nickel or iron, or to find a catalyst from a different block in the periodic table that is both abundant and can also react the way that metals do."

磷和膦为何重要

Why phosphorus and phosphines matter

磷是生命必需的元素。因此，含磷化合物在自然界中非常常见，并在有机化学中被广泛使用。

Phosphorus is an element essential to life. Phosphorous compounds are therefore very common in nature and widely used in organic chemistry.

"化学家已经开发了各种使用磷化合物的命名反应，包括膦作为催化剂的例子，"Doyle说。

"Chemists have developed all sorts of named reactions using phosphorus compounds, including examples where phosphines serve as catalysts," said Doyle.

膦是磷原子与三个碳原子键合的分子。"但我们发现了一种新的磷反应模式，模仿钯和铱等过渡金属在催化中常见的模式，"Doyle说。

Phosphines are molecules containing a phosphorus atom bonded with three carbon atoms. "But we've discovered a new reactivity mode for phosphorus that mimics a mode that transition metals like palladium and iridium commonly perform in catalysis," Doyle said.

实验室中的意外发现

A surprise discovery in the lab

Doyle实验室发现光可用于将膦转化为能够替代稀有昂贵催化剂的物质，这是在尝试形成碳氮键的方法时偶然获得的意外结果。

The Doyle lab's discovery that light could be used to transform phosphines into something that could do the work of rarer and expensive catalysts was the serendipitous result of experimenting with ways to form carbon-nitrogen bonds.

"我们惊讶地发现，对于与我们预期完全不同的产物却表现出高反应活性。弄清楚发生了什么是个谜，"first作者、博士生范弗洛拉（Flora Fan）说。虽然最初并非为此设计，但团队最终确定磷在反应中必须像金属一样起作用。

"We were surprised to see high reactivity for a completely different product than what we expected. It was definitely a puzzle to try to figure out what was going on," said first author and doctoral student Flora Fan. Though initially not designed to perform this way, the team eventually determined that phosphorus had to be working like a metal in the reaction.

该反应通过一种寿命短、高反应活性的磷形式进行。这种形式可以通过与金属催化剂活化这些双键的方式非常相似的途径与碳碳双键反应。虽然膦模仿了金属催化剂的行为，但它也遵循根本不同的规则。

The reaction proceeds through a short-lived, highly reactive form of phosphorus. This form can react with carbon-carbon double bonds through pathways that closely resemble the ways metal catalysts activate these double bonds. While the phosphine mimics the behavior of metal catalysts, it also operates by fundamentally different rules.

关键区别在于，膦起始状态可以进行涉及转移一个和两个电子的反应，而过渡金属催化剂通常涉及转移两个电子。因此，氢胺化反应遵循独特的路线，能够使用更多样化的含氮化合物。

The key difference is that the phosphine starts in a state that can undergo reactions that involve the transfer of both one and two electrons, whereas transition metal catalysts most commonly involve the transfer of two electrons. Because of this, the hydroamination reaction follows a unique route that enables more diverse nitrogen-containing compounds to be used.

这对未来药物意味着什么

What this could mean for future drugs

Doyle团队希望这些反应活性的相似性和差异性能激发基于磷催化剂设计化学反应的新策略。

Doyle's team hopes that these similarities and differences in reactivity inspire new strategies with phosphorus-based catalysts for designing chemical reactions.

"我们很兴奋能尝试了解能将这种化学推进多远，"范弗洛拉说。"希望它能为制造药物化合物和其他高附加值化学品打开更多通用方法的大门。"

"We're excited about trying to understand how far we can take this chemistry," said Fan. "Hopefully, it will open doors to more versatile methods for making drug compounds and other value-added chemicals."

与此同时，汽车车主可以期待这一发现最终应用于不再吸引盗贼的催化转化器。

Meanwhile, automobile owners can hope that the discovery eventually finds its way into catalytic converters that no longer appeal to thieves.