Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 3, 2012
Previous Article Next Article

Electrophilic and nucleophilic enzymatic cascade reactions in biosynthesis

Author affiliations

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

Back to tab navigation

Article information


Submitted
11 Oct 2011
First published
03 Feb 2012

Nat. Prod. Rep., 2012,29, 337-350
Article type
Review Article

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

Social activity

Search articles by author

Spotlight

Advertisements