Bond-Weakening Catalysis: Conjugate Aminations Enabled by the Soft Homolysis of Strong N-H Bonds

Journal of the American Chemical Society

Volumn 137, Issue 20, 2015, Pages 6440-6443

  Tarantino, Kyle T ^a   Miller, David C ^a   Callon, Ted A ^a   Knowles, Robert R ^a  

^a PRINCETON UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; COORDINATION REACTIONS; ELECTRON TRANSPORT PROPERTIES; METALS; REDOX REACTIONS;

ARYL AMIDE; CLOSED SHELLS; HOMOLYSIS; NEUTRAL CONDITIONS; PROTON COUPLED ELECTRON TRANSFERS; REDOX ACTIVE METAL CENTERS; SUBSTRATE ACTIVATION; TITANOCENE COMPLEXES;

AMINATION;

HYDROGEN; TITANOCENE; AMIDE;

AMINATION; ARTICLE; CATALYSIS; CATALYST; COMPLEX FORMATION; CONJUGATE; CONTROLLED STUDY; CYCLIZATION; DISSOCIATION; ELECTRON TRANSPORT; HYDROGEN BOND; CHEMICAL STRUCTURE; CHEMISTRY; SYNTHESIS;

AMIDES; AMINATION; CATALYSIS; MOLECULAR STRUCTURE;

EID: 84930226954     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/jacs.5b03428     Document Type: Article

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47. Alternatively, direct HAT from TEMPO-H to the Ti(IV) enolate in Scheme 1 is calculated to be favorable by 14 kcal/mol and is a plausible alternative mechanism for regeneration of the Ti(III) catalyst and TEMPO. See Supporting Information (SI) for details.
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53. 3, a non-redox-active Lewis acid, is calculated to be 99 kcal/mol.
54. All thermochemical parameters were also calculated using the LANL2DZ functional, with very similar results. See SI.
55. See SI for details.
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