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Issue 3, 2012
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Electrophilic and nucleophilic enzymatic cascade reactions in biosynthesis

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Abstract

Covering: up to 2011

The biosynthesis of cyclic terpenoids and polyethers involves enzyme-initiated cascade reactions for ring formation. While the former are obtained by electrophilic cascades through carbenium ions as intermediates, cyclic polyethers are formed by nucleophilic cascade reactions of (poly)epoxide precursors. These mechanistically complementary pathways follow common principles via (i) triggering of the cascade by forming a reactive intermediate (‘initiation’), (ii) sequential ‘proliferation’ of the cyclization and finally (iii) ‘termination’ of the cascade. As analyzed in this concept paper, the multiplicity of precursors, combined with various initiation and termination routes and kinetically favored or disfavored cyclization modes accounts for the enormous diversity in cyclic terpenoid and polyether scaffolds. Although the essential role of enzymes in the triggering of these cascades is reasonably well understood, remarkably little is known about their influence in proliferation reactions, especially those implying kinetically disfavored (anti-Markovnikov and anti-Baldwin) routes. Mechanistic analysis of enzymatic cascade reactions provides biomimetic strategies for natural product synthesis.

Graphical abstract: Electrophilic and nucleophilic enzymatic cascade reactions in biosynthesis

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Publication details

The article was received on 11 Oct 2011 and first published on 03 Feb 2012


Article type: Review Article
DOI: 10.1039/C2NP00078D
Citation: Nat. Prod. Rep., 2012,29, 337-350
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    Electrophilic and nucleophilic enzymatic cascade reactions in biosynthesis

    B. T. Ueberbacher, M. Hall and K. Faber, Nat. Prod. Rep., 2012, 29, 337
    DOI: 10.1039/C2NP00078D

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