Reaction mechanisms

Definition

A reaction mechanism is a sequence of elementary reactions that can explain how an overall chemical reaction proceeds.

Latest Research and Reviews

  • Reviews |

    Our increasing understanding of non-covalent interactions involving aromatic systems is reviewed, and the use of these insights in the design of small-molecule catalysts and enzymes is surveyed.

    • Andrew J. Neel
    • , Margaret J. Hilton
    • , Matthew S. Sigman
    •  & F. Dean Toste
    Nature 543, 637–646
  • Research | | open

    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.

    • Yoshihiro Sohtome
    • , Genta Nakamura
    • , Atsuya Muranaka
    • , Daisuke Hashizume
    • , Sylvain Lectard
    • , Teruhisa Tsuchimoto
    • , Masanobu Uchiyama
    •  & Mikiko Sodeoka
  • Research | | open

    Regioselectivity during electrophilic aromatic substitution is typically controlled by substituents on the aryl group. Here the authors report an electrophilic aromatic substitution reaction, wherein remote chiral ester groups direct the electrophile to a precise location on the molecule.

    • Kyle E. Murphy
    • , Jessica L. Bocanegra
    • , Xiaoxi Liu
    • , H.-Y. Katharine Chau
    • , Patrick C. Lee
    • , Jianing Li
    •  & Severin T. Schneebeli
  • Research | | open

    A key step in the on-surface synthesis of graphene nanoribbons is thermal annealing of polymer precursors on a metal substrate. Here, Ma et al. decouple the cyclodehydrogenation reaction from the catalytic metal substrate and grow graphene nanoribbons by injecting charges at molecular sites.

    • Chuanxu Ma
    • , Zhongcan Xiao
    • , Honghai Zhang
    • , Liangbo Liang
    • , Jingsong Huang
    • , Wenchang Lu
    • , Bobby G. Sumpter
    • , Kunlun Hong
    • , J. Bernholc
    •  & An-Ping Li
  • Research | | open

    Finding catalyst mechanisms remains a challenge due to the complexity of hydrocarbon chemistry. Here, the authors shows that scaling relations and machine-learning methods can focus full-accuracy methods on the small subset of rate-limiting reactions allowing larger reaction networks to be treated.

    • Zachary W. Ulissi
    • , Andrew J. Medford
    • , Thomas Bligaard
    •  & Jens K. Nørskov

News and Comment

  • News and Views |

    '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.

    • David A. Fulton
    Nature Chemistry 8, 899–900
  • News and Views |

    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.

    • Arthur Winter
    Nature Chemistry 7, 473–475
  • News and Views |

    The synthesis and isolation of a silane adduct of an electrophilic boron species provides insight into the mechanism of metal-free catalytic reductions based on frustrated Lewis pairs.

    • Douglas W. Stephan
    Nature Chemistry 6, 952–953
  • News and Views |

    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.

    • Charles E. Hornsby
    •  & Robert S. Paton
    Nature Chemistry 6, 88–89