DNA作催化剂:小分子体外不对称催化合成

DNA as catalyst: catalytic in vitro asymmetric syntheses of small molecules

综述了以插入非手性二价铜配合物的鲑鱼精DNA(st-DNA)作为催化剂,于体外催化包括不对称DielsAlder反应、Friedel-Crafts反应与Michael加成等一系列小分子反应的研究进展。这些反应在天然产物与其他具生物活性物质合成途径设计中有重要作用。反应通常可以取得大于80%的对映体过量百分数(ee)值,并于优化后可进一步提高到90%至99%。DNA的碱基序列对对映选择性将产生影响,且因配体结构而异,有较多G或C相连的DNA序列通常可以产生较好的对映选择性。

This paper reviews recent works on in vitro asymmetric catalysis of small molecules,with salmon testes DNA（ st-DNA） inserted by achiral Cu（ II） complexes as catalysts. Possible reaction types include Diels-Alder Reaction,Friedel-Crafts Reaction and Michael Addition that are crucial for synthetic route design of natural products and other biologically active compounds. These reactions usually obtain fairly high enantiomeric excess（ ee） of over 80%. After optimization,the ee value can further increase to 90% to 99%.The base sequence of DNA will affect the enantioselectivity in ways differ with the ligand structure. Generally,a DNA molecule with more continuous G or C sequence has better enantioselectivity.