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Stabilization of a Chiral Dirhodium Carbene by Encapsulation and a Discussion of the Stereochemical Implications

MPS-Authors
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Werlé,  Christophe
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Goddard,  Richard
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Philipps,  Petra
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Farès,  Christophe
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Werlé, C., Goddard, R., Philipps, P., Farès, C., & Fürstner, A. (2016). Stabilization of a Chiral Dirhodium Carbene by Encapsulation and a Discussion of the Stereochemical Implications. Angewandte Chemie International Edition, 55(36), 10760-10765. doi:10.1002/anie.201605502.


Cite as: https://hdl.handle.net/11858/00-001M-0000-002B-60E3-6
Abstract
For the first time, the stereochemical course of an asymmetric cyclopropanation can be discussed on the basis of experimental structural information on a pertinent chiral dirhodium carbene intermediate. Key to success was the formation of racemic single crystals of a heterochiral [Rh2{(S*)-PTTL}4{=C(Ar)COOMe}][Rh2{(R*)-PTTL}4] (Ar=MeOC6H4; PTTL=N-phthaloyl-tert-leucinate) capsule, which has been characterized by X-ray diffraction. NMR spectroscopic data confirm that the obtained structural portrait is also relevant in solution and provide additional information about the dynamics of this species. The chiral binding pocket is primarily defined by the conformational preferences of the N-phthaloyl-protected amino acid ligands and reinforced by a network of weak interligand interactions that get stronger when chlorinated phthalimide residues are used.