Publication Date:
2016-01-20
Description:
A self-assembled supramolecular complex is reported to catalyze alkyl-alkyl reductive elimination from high-valent transition metal complexes [such as gold(III) and platinum(IV)], the central bond-forming elementary step in many catalytic processes. The catalytic microenvironment of the supramolecular assembly acts as a functional enzyme mimic, applying the concepts of enzymatic catalysis to a reactivity manifold not represented in biology. Kinetic experiments delineate a Michaelis-Menten-type mechanism, with measured rate accelerations (k(cat)/k(uncat)) up to 1.9 x 10(7) (here k(cat) and k(uncat) are the Michaelis-Menten enzymatic rate constant and observed uncatalyzed rate constant, respectively). This modality has further been incorporated into a dual catalytic cross-coupling reaction, which requires both the supramolecular microenvironment catalyst and the transition metal catalyst operating in concert to achieve efficient turnover.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Kaphan, David M -- Levin, Mark D -- Bergman, Robert G -- Raymond, Kenneth N -- Toste, F Dean -- R01 GM073932/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 2015 Dec 4;350(6265):1235-8. doi: 10.1126/science.aad3087. Epub 2015 Dec 3.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA. ; Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA. ; Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA. rbergman@berkeley.edu raymond@socrates.berkeley.edu fdtoste@berkeley.edu.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/26785485" target="_blank"〉PubMed〈/a〉
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
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Chemistry and Pharmacology
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Computer Science
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Medicine
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Natural Sciences in General
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Physics
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