A Nuclearity‐Dependent Enantiodivergent Epoxide Opening via Enthalpy‐Controlled Mononuclear and Entropy‐Controlled Dinuclear (Salen)Titanium Catalysis

• Published in: Angewandte Chemie International Edition Vol. 62; no. 37; pp. e202309525 - n/a
• Main Authors: Li, Shengxiao, Zhu, Hui, Li, Longfei, Chen, Wanjiao, Jiang, Jie, Qu, Zheng‐Wang, Grimme, Stefan, Zhang, Yong‐Qiang
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 11.09.2023; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Catalysis; Catalysts; Chemistry; Chemistry, Multidisciplinary; Coordination compounds; Enantiodivergent; Enthalpy; Entropy; Epoxide Opening; Metal complexes; Nuclearity-Dependent; Physical Sciences; Radical; Science & Technology; Self-assembly; Titanium; Titanium Catalysis; ENANTIOSELECTIVITY; Enantiodivergent; CONFORMATIONAL FLEXIBILITY; ASYMMETRIC ADDITION; ZETA-VALENCE QUALITY; Radical; MICHAEL ADDITION; REVERSAL; Nuclearity-Dependent; Titanium Catalysis; BASIS-SETS; METAL; Epoxide Opening; FRIEDEL-CRAFTS REACTION; TRIMETHYLSILYL CYANIDE
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202309525

A nuclearity‐dependent enantiodivergent epoxide opening reaction has been developed, in which both antipodes of chiral alcohol products are selectively accessed by mononuclear (salen)TiIII complex and its self‐assembled oxygen‐bridged dinuclear counterparts within the same stereogenic ligand scaffold. Kinetic studies based on the Eyring equation revealed an enthalpy‐controlled enantio‐differentiation mode in mononuclear catalysis, whereas an entropy‐controlled one in dinuclear catalysis. DFT calculations outline the origin of the enantiocontrol of the mononuclear catalysis and indicate the actual catalyst species in the dinuclear catalytic system. The mechanistic insights may shed a light on a strategy for stereoswichable asymmetric catalysis utilizing nuclearity‐distinct transition‐metal complexes. A nuclearity‐dependent enantiodivergent epoxide opening reaction has been developed based on a mononuclear (salen)TiIII complex and its self‐assembled oxygen‐bridged dinuclear counterparts within the same stereogenic ligand scaffold. Mechanistic studies reveal that the nuclearity‐distinct catalysts regulate the enthalpy and entropy controlling modes in the enantiodifferentiation process to achieve profound chirality inversion.