Chao Yang, Subramaniam Muthusamy, Namitharan Kayambu, Zhu Yumei, Koolma Victor, Hao Zitong, Li Shikang, Wang Yaxin, Hudoynazarov Ilyos, Miloserdov Fedor M, Zuilhof Han
School of Pharmaceutical Science and Technology, Tianjin University, 92 Weijin Road, Tianjin 300072, China.
Laboratory of Organic Chemistry, Wageningen University, Stippeneng 4, 6708WE Wageningen, The Netherlands.
J Org Chem. 2023 Nov 17;88(22):15658-15665. doi: 10.1021/acs.joc.3c01656. Epub 2023 Oct 30.
Here we report the first asymmetric synthesis of large chiral macrocycles with chiral sulfur atoms. Building on stereospecific SuFEx and SuPhenEx click chemistries, this approach utilizes disulfonimidoyl fluorides and disulfonimidoyl -nitrophenolates─which are efficient building blocks with two chiral sulfur centers, and diphenols to efficiently form novel S-O bonds. Characteristic results include the enantiospecific one-step synthesis of rings consisting of 21-58 members and characterization of both enantiomers ( and ) by e.g. X-ray crystallography.
在此，我们报道了首例含手性硫原子的大型手性大环化合物的不对称合成。基于立体专一性的硫氟交换（SuFEx）和硫酚交换（SuPhenEx）点击化学，该方法利用二磺酰亚胺基氟化物和二磺酰亚胺基 - 硝基酚盐（它们是具有两个手性硫中心的高效构建单元）与双酚，有效地形成了新型S-O键。典型结果包括对由21至58个成员组成的环进行对映体特异性一步合成，并通过例如X射线晶体学对两种对映体（和）进行表征。
