Highly Enantioselective Carbonyl–Ene Reactions of 2,3-Diketoesters: Efficient and Atom-Economical Process to Functionalized Chiral α-Hydroxy-β-Ketoesters†
Phong M. Truong
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA)
Search for more papers by this authorDr. Peter Y. Zavalij
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA)
Search for more papers by this authorCorresponding Author
Prof. Michael P. Doyle
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA)
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA)Search for more papers by this authorPhong M. Truong
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA)
Search for more papers by this authorDr. Peter Y. Zavalij
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA)
Search for more papers by this authorCorresponding Author
Prof. Michael P. Doyle
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA)
Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742 (USA)Search for more papers by this authorSupport for this research from the National Science Foundation (CHE 1212446) is gratefully acknowledged.
Graphical Abstract
Outside the box: Carbonyl–ene reactions of 2,3-diketoesters, catalyzed by [Cu{(S,S)-tBu-box}](SbF6)2 [box=bis(oxazoline)], generate chiral α-functionalized α-hydroxy-β-ketoesters in up to 94 % yield and 97 % ee. The 2,3-diketoesters are conveniently accessed from the corresponding α-diazo-β-ketoester, and a catalyst loading as low as 1.0 mol % can be used.
Abstract
Carbonyl–ene reactions of 2,3-diketoesters catalyzed by [Cu{(S,S)-tBu-box}](SbF6)2 [box=bis(oxazoline)] generate chiral α-functionalized α-hydroxy-β-ketoesters in up to 94 % yield and 97 % ee. The 2,3-diketoesters are conveniently accessed from the corresponding α-diazo-β-ketoester, and a catalyst loading as low as 1.0 mol % can be achieved.
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