DNA-based asymmetric catalysis: Sequence-dependent rate acceleration and enantioselectivity
DNA-based asymmetric catalysis: Sequence-dependent rate acceleration and enantioselectivity
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DOI：
10.1021/ja803170m
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发表时间：
2008-09-03
影响因子：
15
通讯作者：
Roelfes, Gerard
中科院分区：
文献类型：
--
作者：
Boersma, Arnold J.;Klijn, Jaap E.;Roelfes, Gerard
本研究表明，在氮杂查尔酮与环戊二烯的基于DNA的对映选择性Diels-Alder反应中，DNA的作用不仅限于手性支架。DNA与4，4 '-二甲基-2，2'-联吡啶的铜络合物（Cu-L1）的组合与单独的Cu-L1催化相比产生高达2个数量级的速率加速。此外，对映体选择性和速率增强被证明是依赖于DNA序列。这些特征是在Diels-Alder反应中用鲑鱼睾丸DNA/Cu-L1观察到的高效和对映选择性催化的主要原因。事实上，绝对水平的立体控制，可以实现一个简单的和弱的DNA结合复合物，如Cu-L1是一个明确的证明的权力的超分子方法混合催化。
This study shows that the role of DNA in the DNA-based enantioselective Diels-Alder reaction of azachalcone with cyclopentadiene is not limited to that of a chiral scaffold. DNA in combination with the copper complex of 4,4'-dimethyl-2,2'-bipyridine (Cu-L1) gives rise to a rate acceleration of up to 2 orders of magnitude compared to Cu-L1 catalysis alone. Furthermore, both the enantioselectivity and the rate enhancement prove to be dependent on the DNA-sequence. These features are the main reasons for the efficient and enantioselective catalysis observed with salmon testes DNA/Cu-L1 in the Diels-Alder reaction. The fact that absolute levels of stereocontrol can be achieved with a simple and weak DNA-binding complex like Cu-L1 is a clear demonstration of the power of the supramolecular approach to hybrid catalysis.