Volume 3, Issue 1, Pages 174-191 (July 2017) Artificial Chiral Metallo-pockets Including a Single Metal Serving as Structural Probe and Catalytic Center  Pinglu Zhang, Coralie Tugny, Jorge Meijide Suárez, Maxime Guitet, Etienne Derat, Nicolas Vanthuyne, Yongmin Zhang, Olivia Bistri, Virginie Mouriès-Mansuy, Mickaël Ménand, Sylvain Roland, Louis Fensterbank, Matthieu Sollogoub  Chem  Volume 3, Issue 1, Pages 174-191 (July 2017) DOI: 10.1016/j.chempr.2017.05.009 Copyright © 2017 Elsevier Inc. Terms and Conditions

Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 1 Representation of a Carbene-Capped Cyclodextrin Metal Complex Characterized by a Well-Defined Placing of the Metal Inside the Cavity The carbene (NHC) is represented in blue. The cyclodextrin macrocycle is shown in beige. Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 2 Presentation of All Carbene-Capped CDs Studied Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 3 NCI Analysis of (α-ICyD)AgCl The molecular structure is displayed by the yellow backbone, and the NCI layers are color coded as follows: blue, strong interactions; green, weak interactions; and red, repulsive interactions. (1) Anagostic interactions between H-5s and Ag, green circles; (2) weak hydrogen bonds between H-3s and Cl, red circles. Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 4 Superimposition of Modeled (α-ICyD)AgCl DFT, green; molecular mechanics, blue. Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 5 Models of (α-ICyD)AgCl, (β-ICyD)AgCl, (α-TriCyD)AgCl, (γ-A,E-ICyD)AgCl, and (γ-A,D-ICyD)AgCl Ag to H-5s distances (in green) and Cl to H-3s distances (in red) are ordered according to their chemical shifts. Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 6 Estimated Average Shapes, Connolly Surface, in Solutions of (α-ICyD)MCl, (β-ICyD)MCl, (α-TriCyD)MCl, (γ-A,E-ICyD)MCl, and (γ-A,D-ICyD)MCl Arrows indicate the groove, the narrow side, or the M-helix side. Cl has been omitted for clarity. Me groups are oriented in the same direction for comparison purposes. Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 7 Rationalization of the Enantioselectivities in the Cycloisomerization of 6 (A) Possible approaches of 6 on (α-ICyD)Au. The sterically favored approach is in green, and the sterically unfavored approach is in red. (B) The corresponding simplified model. (C) Possible approaches of 6 on (β-ICyD)Au. The sterically favored approach is in green, and the sterically unfavored approach is in red. (D) The corresponding simplified model. Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Scheme 1 General Synthetic Scheme Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Scheme 2 Gold-Catalyzed Regioselective Cycloisomerization of Enyne 1 Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Scheme 3 Proposed Mechanism of the Gold-Catalyzed Regioselective Cycloisomerization of Enyne 1 Using α-ICyD Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Scheme 4 Proposed Mechanism of the Gold-Catalyzed Regioselective Cycloisomerization of Enyne 1 Using β-ICyD Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions

Scheme 5 Gold-Catalyzed Enantioselective Cycloisomerizations of Enynes 5 and 6 Chem 2017 3, 174-191DOI: (10.1016/j.chempr.2017.05.009) Copyright © 2017 Elsevier Inc. Terms and Conditions