High Activity and Efficient Turnover by a Simple, Self-Assembled "Artificial Diels-Alderase"

被引：166

作者：

Marti-Centelles, Vicente ^{[1
]}

Lawrence, Andrew L. ^{[1
]}

Lusby, Paul J. ^{[1
]}

机构：

[1] Univ Edinburgh, EaStCHEM Sch Chem, Joseph Black Bldg,David Brewster Rd, Edinburgh EH9 3FJ, Midlothian, Scotland

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 08期

关键词：

SUPRAMOLECULAR CATALYSIS; NONCOVALENT CATALYSIS; BASIC SOLUTION; CAVITY; CAGES; CYCLIZATION; SOLVENTS; ENZYME; WATER;

D O I：

10.1021/jacs.7b12146

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The Diels-Alder (DA) reaction is a cornerstone of synthesis, yet Nature does not use catalysts for intermolecular [4+2] cycloadditions. Attempts to create artificial "Diels-Alderases" have also met with limited success, plagued by product inhibition. Using a simple Pd2L4 capsule we now show DA catalysis that combines efficient turnover alongside enzyme-like hallmarks. This includes excellent activity (k(cat)/k(uncat) > 10(3)), selective transition-state stabilization comparable to the most proficient DA catalytic antibodies, and control over regio- and chemoselectivity 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.

引用

页码：2862 / 2868

页数：7