Yamani Khalil, Pierre Hugo, Archambeau Alexis, Meyer Christophe, Cossy Janine
Molecular, Macromolecular Chemistry, and Materials, ESPCI Paris, PSL University, CNRS, 10 rue Vauquelin, 75005, Paris, France.
Angew Chem Int Ed Engl. 2020 Oct 12;59(42):18505-18509. doi: 10.1002/anie.202008572. Epub 2020 Aug 25.
Catalytic enantioselective access to disubstituted functionalized gem-difluorocyclopropanes, which are emerging fluorinated motifs of interest in medicinal chemistry, was achieved through asymmetric transfer hydrogenation of gem-difluorocyclopropenyl esters, catalyzed by a Noyori-Ikariya (p-cymene)-ruthenium(II) complex, with (N-tosyl-1,2-diphenylethylenediamine) as the chiral ligand and isopropanol as the hydrogen donor. The resulting cis-gem-difluorocyclopropyl esters were obtained with moderate to high enantioselectivity (ee=66-99 %), and post-functionalization reactions enable access to valuable building blocks incorporating a cis- or trans-gem-difluorocyclopropyl motif.
通过诺伊里-池谷（对异丙基苯）-钌（II）配合物催化偕二氟环丙烯基酯的不对称转移氢化反应，以（N-对甲苯磺酰基-1,2-二苯基乙二胺）作为手性配体，异丙醇作为氢供体，实现了对二取代官能化偕二氟环丙烷的催化对映选择性合成，偕二氟环丙烷是药物化学中新兴的氟化基序。所得的顺式偕二氟环丙基酯以中等至高对映选择性（ee = 66 - 99%）获得，并且后官能化反应能够获得包含顺式或反式偕二氟环丙基基序的有价值的结构单元。
