” This is a rare example of a discovery of a new catalytic reaction, and it opens a real wealth of new chances to do chemistry enabled by a reaction that never ever existed before,” says Christopher Cummins, the Henry Dreyfus Professor of Chemistry at MIT and the senior author of the research study.
These phosphorus-containing rings could discover uses as drivers for other reactions, or as precursors for useful compounds such as pharmaceuticals, Cummins states.
MIT graduate student Martin-Louis Riu is the lead author of the paper, released this week in the Journal of the American Chemical Society. Previous MIT research study fellow Andre Eckhardt is likewise an author of the research study.
Developing a ring
Organic compounds that contain double bonds between carbon atoms, also understood as alkenes or olefins, are necessary precursors in many industrially beneficial chain reaction. By breaking those carbon-carbon bonds and adding brand-new atoms or groups of atoms, researchers can produce a variety of brand-new products.
As one example, chemists have actually formerly created methods to convert a carbon-carbon double bond into a three-membered ring by including either another carbon atom, a nitrogen atom, or an oxygen atom. Such substances can be discovered in plastics, pharmaceuticals, textiles, and other beneficial items.
However, since phosphorus is much heavier than carbon, oxygen, or nitrogen, it has been tough to find a way to integrate it into olefins without utilizing “brute force” methods that require extreme chemical conditions. The MIT team wished to create a method to perform this reaction under moderate conditions, utilizing a catalyst to transfer a phosphinidene group– a phosphorus atom bound to a natural chemical group– to the olefin.
In order to accomplish that, they required a beginning material that could function as a source of phosphinidene, but such compounds did not exist since direct analogues of those used for lighter components such as carbon are unsteady with phosphorus.
In a 2019 paper, Cumminss lab established one possible source, including phosphinidene connected to a molecule that includes numerous hydrocarbon rings. Utilizing this compound, they had the ability to manufacture a three-membered ring containing phosphorus, however the reaction needed high temperatures and only dealt with specific kinds of olefins.
In their new paper, the MIT team utilized a different source of phosphorus for the response– a substance that Cummins lab first manufactured in 2021. This particle is a tetrahedron, a shape that naturally has a terrific offer of energy “pressure,” similar to a compressed spring, due to the fact that of the small bond angles in between the 4 atoms that form the tetrahedron.
This substance, called tri-tert-butylphosphatetrahedrane, has three vertices consisting of carbon atoms connected to a chemical group called tert-butyl, and one vertex consisting of a phosphorus atom with an unshared pair of electons. Under the ideal conditions, this stretched molecule can be disintegrated to release the phosphorus atom.
Efficient synthesis
Using this spring-loaded particle, the scientists were able to utilize a nickel-containing driver to transfer phosphinidene to olefins to create three-membered rings. This response can be done at space temperature level, with high yield of the preferred product.
” All the stars aligned here in regards to us being able to manufacture an extremely stretched precursor that leads to room temperature level reactivity and fast catalysis,” Cummins says.
The researchers now prepare to further examine the mechanism of how this response takes place, which they think depends on phosphinidene being temporarily moved to the nickel driver complex. The catalyst then integrates the phosphorus into the double bond of the olefin.
They likewise hope to explore the possibility of creating a range of new compounds that include the phosphorus-containing ring, and to develop ways to control which of two possible mirror image versions are manufactured. Once these phosphorus-containing rings are formed, they can be opened by including additional particles to produce other useful substances. Prospective applications for these sort of products include drivers for other reactions, or parts of pharmaceuticals that contain phosphorus.
Referral: “Reactions of Tri-tert-Butylphosphatetrahedrane as a Spring-Loaded Phosphinidene Synthon Featuring Nickel-Catalyzed Transfer to Unactivated Alkenes” by Martin-Louis Y. Riu, André K. Eckhardt and Christopher C. Cummins, 19 April 2022, Journal of the American Chemical Society.DOI: 10.1021/ jacs.2 c02236.
The research was funded by the National Science Foundation and a Feodor Lynen Research Fellowship from the Alexander von Humboldt Foundation.
MIT chemists found a way to include phosphorus into three-membered ring compounds, utilizing this “spring-loaded” molecule as the source of phosphorus. Credit: Courtesy of the scientists
The reaction, which is an alternative to procedures that require severe chemical conditions, provides a brand-new course to producing important phosphorus-containing molecules.
MIT chemists have designed a new chemical reaction that permits them to synthesize a phosphorus-containing ring, utilizing a driver to add phosphorus to basic organic substances called alkenes.
Their response, which yields a ring including two carbon atoms and one phosphorus atom, can be performed at normal temperature and pressure, and uses an unique “spring-loaded” phosphorus-containing molecule that supplies the phosphorus atom.
