Beilstein J. Org. Chem.2025,21, 421–443, doi:10.3762/bjoc.21.30
concepts of organization and polarization, and anticipating future developments; and, (2) to introduce robust organic cages as functional enzyme mimics, and highlight how their unique features might advance cavity catalysis and provide more realistic enzymemodels for studying electric field catalysis and
smaller reagents.
Also in the category of (functionalized) macrocycles are large enzymemodels, such as those reported by Cram [65][86][87][88], Breslow [74][75][89][90][91][92], Diederich [93], and others [94][95][96], constructed by (often laborious) linear synthesis to afford more elaborate
combinations of macrocyclic cavities adorned with functional groups (Figure 3A) [97][98]. These grand “set-piece” enzymemodels typically showed only modest catalytic enhancements for enzyme-relevant reactions like the hydrolysis of activated esters, and so mostly contributed to the view that enzymes do not
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Graphical Abstract
Figure 1:
Catalytic rate enhancements from a reduction in the Gibbs free energy transition barrier can be fra...
Beilstein J. Org. Chem.2017,13, 2332–2339, doi:10.3762/bjoc.13.230
acetylene. A critical assessment of, and a possible explanation for the earlier reported results are offered. The title question is answered with "no".
Keywords: acetylene hydratase; alkynes; catalytic hydration; enzymemodels; tungsten complexes; Introduction
In 1985, the enzyme acetylene hydratase
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Graphical Abstract
Scheme 1:
a) Acetylene hydratase catalyzes the hydration of acetylene to ethanal. b) Currently favored key-st...