Zirconium bis(amido) catalysts for asymmetric intramolecular alkene hydroamination

Organometallics

Volumn 25, Issue 20, 2006, Pages 4731-4733

  Watson, Donald A ^a   Chiu, Melanie ^a   Bergman, Robert G ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

HYDROAMINATION CATALYSTS; INTRAMOLECULAR ALKENE HYDROAMINATION; PIPERIDINES; PYRROLIDINES;

AMINATION; COMPLEXATION; OLEFINS; ZIRCONIUM COMPOUNDS;

CATALYSTS;

EID: 33749828529     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0606791     Document Type: Article

References (30)

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21. There has been one report of an asymmetric intramolecular allene hydroamination catalyzed by neutral titanium bis(amido) complexes that employed chiral amino alcohol ligands. The maximum reported ee was 16%. See: Hoover, J. M.; Petersen, J. R.; Pikul, J. H.; Johnson, A. R. Organometallics 2004, 23, 4614-4620.
22. In screening efforts, ligand (22 mol %) and group IV tetrakis- (dimethylamide) (20 mol %) were combined in toluene and heated to 135°C for 15 min to ensure formation of ligand/metal complex. Aminoalkene 1 was then introduced, and the reaction mixture was heated with stirring for 24 h. After acylation with trifluoroacetyl anhydride (TFAA), the product was analyzed by chiral GC.
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28. To our knowledge, these are the first examples of hafnium-catalyzed hydroaminations.
29. See Supporting Information for details.
30. 2 does not inhibit the reaction excludes the possibility that catalysis is due to trace acidic impurities.