Sun Yang, Cramer Nicolai
Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, 1015, Lausanne, Switzerland.
Angew Chem Int Ed Engl. 2018 Nov 19;57(47):15539-15543. doi: 10.1002/anie.201810887. Epub 2018 Oct 26.
Sulfoximines with stereogenic sulfur atoms are attractive structural motifs in drug discovery. A direct catalytic enantioselective method for the synthesis of sulfur-chiral 1,2-benzothiazines from readily accessible diaryl sulfoximines is presented. Rhodium(III) complexes equipped with chiral cyclopentadienyl ligands and paired with suitable carboxylic acid additives engage in an enantiodetermining C-H activation directed by the sulfoximine group. Subsequent trapping of the rhodacycle with a broad range of diazoketones gives access to S-chiral 1,2-benzothiazines with synthetically highly attractive substitution patterns in good yields and enantioselectivities.
具有手性硫原子的磺胺类化合物是药物研发中具有吸引力的结构基序。本文介绍了一种直接催化对映选择性方法，用于从易于获得的二芳基磺胺类化合物合成硫手性1,2-苯并噻嗪。配备手性环戊二烯基配体并与合适的羧酸添加剂配对的铑(III)配合物参与由磺胺基团导向的对映体决定性C-H活化反应。随后，用多种重氮酮捕获铑环，可获得具有合成上极具吸引力的取代模式的S-手性1,2-苯并噻嗪，产率和对映选择性良好。
