Cyclodextrin Cavity‐Induced Mechanistic Switch in Copper‐Catalyzed Hydroboration. Issue 36 (2nd August 2017)

• Record Type: Journal Article
• Authors: Zhang, Pinglu; Meijide Suárez, Jorge; Driant, Thomas; Derat, Etienne; Zhang, Yongmin; Ménand, Mickaël; Roland, Sylvain; Sollogoub, Matthieu
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 36(2017)
• Page Start: 10821
• Page End: 10825
• Publication Date: 2017-08-02
• Subjects: catalysis -- copper -- cyclodextrins -- regioselectivity -- supramolecular chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201705303
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: N ‐heterocyclic carbene‐capped cyclodextrin (ICyD) ligands, α‐ICyD and β‐ICyD derived from α‐ and β‐cyclodextrin, respectively give opposite regioselectivities in a copper‐catalyzed hydroboration. The site‐selectivity results from two different mechanisms: the conventional parallel one and a new orthogonal mechanism. The shape of the cavity was shown not only to induce a regioselectivity switch but also a mechanistic switch. The scope of interest of the encapsulation of a reactive center is therefore broadened by this study. Abstract : Cavity switch : N ‐heterocyclic carbene‐capped cyclodextrin ligands derived from α‐ and β‐cyclodextrins give opposite regioselectivities in a copper‐catalyzed hydroboration. This behavior results from two different mechanisms: the conventional parallel one and a new orthogonal mechanism. The shape of the cavity was shown to induce both a regioselectivity and a mechanistic switch.