If you have an ACS member number, please enter it here so we can link this account to your membership. (optional)

ACS values your privacy. By submitting your information, you are gaining access to C&EN and subscribing to our weekly newsletter. We use the information you provide to make your reading experience better, and we will never sell your data to third party members.



Copper Shines In Asymmetric Amine Synthesis

Photocatalysis: Catalyst based on Earth-abundant metal builds fully substituted stereocenters in reaction initiated by blue light

by Bethany Halford
February 15, 2016 | A version of this story appeared in Volume 94, Issue 7

Molecule makers who want to construct amines adjacent to crowded carbons are getting a blue-light special. Here’s the deal: Chemists at Caltech led by Jonas C. Peters and Gregory C. Fu report they are able to make amines adjacent to fully substituted carbons via a reaction catalyzed by Earth-abundant copper that’s initiated with blue light (Science 2016, DOI: 10.1126/science.aad8313). Such amines are commonly found in natural products, pharmaceuticals, and agrochemicals. What’s more, the reaction is enantioselective, transforming a racemic mixture of a tertiary alkyl chloride into a single amine enantiomer. Peters and Fu believe the reaction proceeds via a radical mechanism. The researchers also point out that a single catalyst is responsible for both the photochemistry and the enantioselective bond formation. Most metal-catalyzed photoredox reactions reported to date use two separate catalysts to accomplish these tasks. “This work stands at a previously unexplored intersection of asymmetric synthesis, catalysis with Earth-abundant metals, photoinduced processes, and cross-coupling reactions of alkyl electrophiles, each of which represents an important current theme in chemical synthesis,” the chemists note.

A scheme showing a tertiary alkyl chloride reacting with a copper catalyst and an amine to produce an amine adjacent to a crowded chiral carbon.


This article has been sent to the following recipient:

Chemistry matters. Join us to get the news you need.