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The competition between chemical reactions critically affects our natural environment and the synthesis of new materials. Here, the authors present an approach to directly image distinct fingerprints of essential organic reactions and monitor their competition as a function of steric substitution.
While ortho-selective C-H activation is well explored, general meta-selective methods are rare and often require directing groups that are retained in the final products. Here the authors show that transient imine groups can be used to direct the meta-functionalization of a range of arenes.
Understanding the interplay between electronic structure and performance and how it relates to mechanism is important for catalysis. Here the authors report an asymmetric [3+2] cycloaddition and show the Ni(II) catalyst possesses a weakly bound acetate ligand, leaving the dz2 orbital partially vacant.
'Click' chemistry allows for the linking together of chemical modules, however, there are currently no methods that also allow for facile 'declicking' to unlink them. Now, a method has been developed to click together amines and thiols, and then allow a chemically triggered declick reaction to release the original molecular components.
Computations of the energetics and mechanism of the Morita–Baylis–Hillman reaction are “not even wrong” when compared with experiments. While computational abstinence may be the purest way to calculate challenging reaction mechanisms, taking prophylactic measures to avoid regrettable outcomes may be more realistic.
High selectivity is essential in the enzymatic biosynthesis of complex natural products. Now, the discovery of multiple sequential bifurcations on the reaction path towards the formation of a diterpenoid shows how dynamics affect selectivity, and suggests how enzymes may steer reactions towards a specific product.