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Enzymes And Metals Enable Regiodivergent Organic Reactions

Judicious choice of engineered enzymes or transition-metal catalysts enables researchers to prepare different products from the same reaction

by Stephen K. Ritter
November 3, 2014 | A version of this story appeared in Volume 92, Issue 44

Reactions schemes showing two pairs catalytic, regioselective reactions.

Divergent regioselectivity, in which the same reaction can lead to different products depending on the catalyst and reaction conditions, is a particular challenge for synthetic organic chemists. Two research teams have reported findings that provide new insight on how to make directional selectivity a little easier. Frances H. Arnold and coworkers at California Institute of Technology engineered two variants of a cytochrome P450BM3 enzyme to control nitrogen atom transfer and enable regiodivergent C–H aminations. One enzyme favors ring-closing amination at the α-position of an alkyl substituent on a benzene sulfonyl azide. The other enzyme favors amination at the β-position (J. Am. Chem. Soc. 2014, DOI: 10.1021/ja509308v). Meanwhile, Chao-Jun Li’s group at McGill University, in Montreal, has discovered a selectivity switch in ring-forming coupling reactions between 2-hydroxybenzaldehydes and terminal alkynes. With a gold catalyst, the researchers obtain an isoflavanone skeleton, whereas a rhodium catalyst produces a coumarin skeleton (Angew. Chem. Int. Ed. 2014, DOI: 10.1002/anie.201407589). According to the researchers, enzymes represent a versatile platform for solving selectivity problems in organic synthesis, either through synthetic biology or through inspiration to develop metal-catalyst enzyme mimics.


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