Highly active chiral ruthenium catalysts for asymmetric ring-closing olefin metathesis

Journal of the American Chemical Society

Volumn 128, Issue 6, 2006, Pages 1840-1846

  Funk, Timothy W ^a   Berlin, Jacob M ^a   Grubbs, Robert H ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; RUTHENIUM; SODIUM COMPOUNDS;

ASYMMETRIC RING-CLOSING METATHESIS (ARCM); CARBENES; ENANTIOSELECTIVITY; REACTIVITY;

OLEFINS;

ALKENE; CARBENE; ETHYLENEDIAMINE; MOLYBDENUM; RUTHENIUM; SILICA GEL; SODIUM IODIDE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL BOND; CHIRALITY; ENANTIOSELECTIVITY; GEL CHROMATOGRAPHY; PROTON NUCLEAR MAGNETIC RESONANCE; REDUCTION; RING CLOSING METATHESIS; RING OPENING; STEREOCHEMISTRY; STEREOSPECIFICITY; TEMPERATURE DEPENDENCE;

ALKENES; CATALYSIS; CYCLIZATION; ETHERS, CYCLIC; ORGANOMETALLIC COMPOUNDS; RUTHENIUM; STEREOISOMERISM;

EID: 33244482255     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja055994d     Document Type: Article

References (48)

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28. Both enantiomers of 1,2-diphenylethylenediamine are commercially available. See Supporting Information for the synthesis of the aryl bromides 7b-d and other experimental details.
29. 2, and an X-ray crystal structure of this complex shows that the isopropyl groups are oriented anti to the phenyl rings on the NHC backbone. See Supporting Information.
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34. (c) Reference 12.
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36. See Supporting Information for more details.
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46. The X-ray crystal structure of an analogue of 2a in ref 3c shows that the plane of the N-bound aryl ring is not orthogonal to the plane of the NHC. QM/MM calculations in ref 19a concluded that the N-bound aryl rings of a substrate-bound ruthenium alkylidene also are not orthogonal to the plane of the NHC.
47. -, the X-Ru-X bond angle also increases. A larger bond angle positions the halides closer to the Ru=CHR moiety (a smaller angle means the halides are pulled away from the alkylidene), which puts the halides in closer proximity to the reacting olefin, creating a smaller pocket, and therefore a more selective reaction. See ref 19a.
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