New arylation inducing reaction developed

15-Jan-2018 - Korea, Republic of (South Korea)

KAIST researchers have identified a reaction mechanism that selectively introduces aryl groups at the desired position of a molecule at room temperature. A team, co-led by Professor Sukbok Chang and Mu-Hyun Baik of the Department of Chemistry, used an iridium catalyst for the reaction. The team also proved that the reaction proceeds by an unusual mechanism by employing computer simulations that were substantiated with targeted experimental probes.

Hydrocarbon is an omnipresent material in nature. But its low reactivity makes it difficult to process to value-added products at the room temperature. Thus, designing catalysts that can accelerate the reaction remains an important challenge in chemistry.

In particular, since most chemicals used in medicine, pharmacy, or material chemistry contain aryl groups, an effective reaction to selectively introduce the aryl group has been an area of intensive research in organic chemistry.

In order to introduce an aryl group into stable carbon-hydrogen (C-H) bond, activation of the C-H bond with a halogen atom or organic metal is required prior to the introduction of the aryl group, or C-H functionalization directly on C-H bond is needed. Direct functionalization is more effective and economical, but most reactions require harsh reaction conditions such as high temperature or excess additives. And adding the aryl fragment selectively to only one among the many possible sites in the molecule is difficult. The new catalyst developed by these KAIST researchers is highly selective.

This work is the latest example of a successful teamwork between experimental and theoretical research groups: Computer simulations revealed that traditional approaches to arylation required high energies because the intermediates produced during the reaction are too low in energy. Based on this insight, the researchers thought of changing the character of the intermediate by oxidizing it, which was predicted to be a great way of increasing the reactivity of the catalyst. Subsequent experimental work showed that this design strategy is highly effective resulting in unprecedented chemical transformations.

Professor Chang said, “We have been able to carry out location-selective arylation at room temperature, as well as identifying a new reaction pathway, different from the conventionally suggested mechanism.” He continued, “This research is significant for identifying the reaction pathway and developing a novel selective reaction method that does not require high temperature or additives based on the mechanistic understanding. This work is a triumph of rational design, rather than fortuitous discovery.”

Original publication

Kwangmin Shin, Yoonsu Park, Mu-Hyun Baik & Sukbok Chang; "Iridium-catalysed arylation of C–H bonds enabled by oxidatively induced reductive elimination"; Nature Chemistry; 2017

https://www.chemeurope.com/en/news/145079/new-arylation-inducing-reaction-developed.html

Original publication

Kwangmin Shin, Yoonsu Park, Mu-Hyun Baik & Sukbok Chang; "Iridium-catalysed arylation of C–H bonds enabled by oxidatively induced reductive elimination"; Nature Chemistry; 2017

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