High Activity and Efficient Turnover by a Simple, Self-Assembled “Artificial Diels–Alderase”

Vicente Martí-centelles, Andrew L. Lawrence, Paul J. Lusby*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The Diels–Alder (DA) reaction is a cornerstone of synthesis, yet Nature does not use catalysts for intermolecular [4+2] cy-cloadditions. Attempts to create artificial “Diels–Alderases” have also met with limited success, plagued by product inhibi-tion. Using a simple Pd2L4 capsule we now show DA catalysis that combines efficient turnover alongside enzyme-like hall-marks. This includes excellent activity (kcat/kuncat > 103), selective transition-state (TS) stabilization comparable to the most proficient DA catalytic antibodies, and control over regio- and chemo-selectivity that would otherwise be difficult to achieve using small-molecule catalysts. Unlike other catalytic approaches that use synthetic capsules, this method is not defined by entropic effects; instead multiple H-bonding interactions modulate reactivity, reminiscent of enzymatic action.
Original languageEnglish
Pages (from-to)2862-2868
Number of pages7
JournalJournal of the American Chemical Society
Volume140
Issue number8
Early online date6 Feb 2018
DOIs
Publication statusPublished - 28 Feb 2018

Keywords

  • SUPRAMOLECULAR CATALYSIS
  • NONCOVALENT CATALYSIS
  • COORDINATION CAGE
  • MOLECULAR CAPSULE
  • BASIC SOLUTION
  • CAVITY
  • WATER
  • HOSTS
  • ENCAPSULATION
  • CYCLIZATION

Fingerprint

Dive into the research topics of 'High Activity and Efficient Turnover by a Simple, Self-Assembled “Artificial Diels–Alderase”'. Together they form a unique fingerprint.

Cite this