Zhu Xin-Qi, Wang Qian, Zhu Jieping
Laboratory of Synthesis and Natural Products (LSPN), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland.
Angew Chem Int Ed Engl. 2023 Jan 2;62(1):e202214925. doi: 10.1002/anie.202214925. Epub 2022 Nov 29.
We report herein the first examples of chiral phosphoric acid-catalyzed enantioselective Diels-Alder reactions between 2-trifluoroacetamido-1,3-dienes 1 and α,β-unsaturated carbonyl compounds 2. Polysubstituted 1-acetamido cyclohexenes 3 were formed in high yields with excellent diastereo- and enantioselectivities. The reaction proceeds through a stepwise process as shown by deuterium labelling experiments. A catalytic enantioselective three-component reaction of 1, 2 and ortho-hydroxybenzhydryl alcohols 4 was subsequently developed furnishing the densely functionalized hexahydroxanthenes 5 in a highly stereoselective manner. This multicomponent reaction generates four chemical bonds with concurrent creation of five contiguous stereocenters.
我们在此报告首例手性磷酸催化的2-三氟乙酰氨基-1,3-二烯1与α,β-不饱和羰基化合物2之间的对映选择性狄尔斯-阿尔德反应。多取代的1-乙酰氨基环己烯3以高产率、优异的非对映选择性和对映选择性生成。氘标记实验表明，该反应通过逐步过程进行。随后开发了1、2与邻羟基二苯甲醇4的催化对映选择性三组分反应，以高立体选择性方式提供了功能密集的六氢呫吨5。这种多组分反应同时生成四个化学键并产生五个相邻的立体中心。
