Zhang Ronghua, Zhu Minghui, Sun Jianwei
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR 999077, China.
J Am Chem Soc. 2025 Oct 8;147(40):36774-36780. doi: 10.1021/jacs.5c12568. Epub 2025 Sep 29.
A family of new spirocyclic chiral mono- and diamine structures has been designed together with their de novo asymmetric synthesis, featuring a short sequence from simple substrates. This study complements the previous limited exploration of the counterparts of well-established 1,1'-spirobiindane-7,7'-diol (SPINOL) and its modified analogs. The convenient enantioselective synthesis of 2,2',3,3'-tetrahydro-1,1'-spirobi-[phenalene]-9,9'-diamine (SPHENAM) and 9'-amino-2,2',3,3'-tetrahydro-1,1'-spirobi[phenalen]-9-ol (NOSPHEN) represents a notable advantage over the limited spirocyclic precedents of this type, which were uniformly derived from their spiro parents. Two synthetic routes, both featuring catalyst-controlled enantioselective induction, have been designed, leading to the convenient construction of a large library of both -symmetric and non--symmetric derivatives of 2,2',3,3'-tetrahydro-1,1'-spirobi[phenalene]-9,9'-diol (SPHENOL), all with high efficiency and enantiomeric excess. Preliminary studies have demonstrated their superior performance as backbones of diverse effective chiral catalysts and ligands, illustrating their potential in asymmetric synthesis.
设计了一类新型螺环手性单胺和二胺结构及其从头不对称合成方法，其特点是从简单底物出发的序列较短。本研究补充了此前对成熟的1,1'-螺二茚-7,7'-二醇（SPINOL）及其修饰类似物对应物的有限探索。2,2',3,3'-四氢-1,1'-螺二[菲]-9,9'-二胺（SPHENAM）和9'-氨基-2,2',3,3'-四氢-1,1'-螺二[菲]-9-醇（NOSPHEN）的便捷对映选择性合成相对于此类有限的螺环先例具有显著优势，这些先例均源自其螺环母体。设计了两条均以催化剂控制对映选择性诱导为特点的合成路线，可方便地构建大量2,2',3,3'-四氢-1,1'-螺二[菲]-9,9'-二醇（SPHENOL）的对称和非对称衍生物库，且均具有高效率和对映体过量。初步研究表明，它们作为多种有效手性催化剂和配体的骨架具有优异性能，展示了其在不对称合成中的潜力。
