徐新芳教授与中山大学胡文浩教授合作在Angew. Chem. Int. Ed. 上发表研究论文

Enantioselective Oxidative Cyclization/Mannich Addition Enabled by Gold(I)/Chiral Phosphoric Acid Cooperative Catalysis

Hanlin Wei1, Ming Bao1, Kuiyong Dong1, Lihua Qiu1, Bing Wu1, Wenhao Hu2,*(胡文浩)and Xinfang Xu1, 2,*(徐新芳)

  

1 Key Laboratory of Organic Synthesis of Jiangsu Province College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou 215123 (China)

2 School of Pharmaceutical Sciences Sun Yat-sen University Guangzhou 510006 (China)

  

Angew. Chem. Int. Ed.2018, 57, 17200 --17204

  

An enantioselective Mannich-type reaction of 3-butynol and nitrones is described, which affords dihydrofuran-3-ones in good yields and with excellent enantioselectivities. The reaction is initiated by gold-catalyzed alkyne oxidation and modification of the resulting gold carbene species with a tethered hydroxy group to form enolate species; the reaction terminates with an enantioselective Mannich-type addition with the assistance of chiral phosphoric acid (CPA) and hydrogen bonding. This novel pattern of alkyne transformation involving chemical bond cleavage, and a fragment modification and reassembly process, provides an atom- and step-economic method, and is the first example of cooperative asymmetric catalysis in gold-catalyzed alkyne oxidations via an a-oxo  gold carbene route.

  

  

  

  

链接:https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201812140