Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University , 21 Nanyang Link, Singapore 637371.
Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University , Huaxi District, Guiyang 550025, People's Republic of China.
Org Lett. 2017 Nov 3;19(21):5892-5895. doi: 10.1021/acs.orglett.7b02883.
A highly enantioselective method for quick access to dihydrocoumarins is reported. The reaction involves a cooperative catalytic process with carbene and in situ generated Brønsted acid as the catalysts. α-Chloro aldehyde and readily available and stable o-hydroxybenzhydryl amine substrates were used to generate reactive azolium ester enolate and ortho-quinone methide (o-QM) intermediates, respectively, to form dihydrocoumarins with exceptionally high diastereo- and enantioselectivities. The catalytic reaction products can be easily transformed to valuable pharmaceuticals and bioactive molecules.
本文报道了一种高对映选择性的快速制备二氢香豆素的方法。该反应涉及一种协同催化过程，其中卡宾和原位生成的布朗斯台德酸分别作为催化剂。α-氯醛和易得且稳定的邻羟基二苯甲胺底物分别生成反应性唑鎓酯烯醇盐和邻醌甲亚胺（o-QM）中间体，从而以极高的非对映选择性和对映选择性形成二氢香豆素。催化反应产物可方便地转化为有价值的药物和生物活性分子。
