Chiral Cooperativity: The Nature of the Diastereoselective and Enantioselective Step in the Gold(I)-Catalyzed Aldol Reaction Utilizing Chiral Ferrocenylamine Ligands

Journal of Organic Chemistry

Volumn 55, Issue 5, 1990, Pages 1649-1664

  Togn, Antonio ^a   Pastor, Stephen D ^a  

^a Ciba Geigy AG ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33751553776     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00292a046     Document Type: Article

References (148)

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124. A referee has pointed out that the Hammett and NMR studies do not necessarily rule out coordination of the carbonyl oxygen atom to the gold(I) atom in the transition state of the rate-determining step, i.e., rate-determining car-bon-carbon bond formation occurs in a transition state containing a tetracoordinate gold(I) atom bonded to two phosphorus atoms, iso-cyanoacetate, and aldehydic oxygen. The lack of change in the 31P NMR spectrum of the gold(I) complex of 4 upon addition of benzaldehyde suggests that prior coordination of the aldehydic oxygen does not occur.
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148. Note Added in Proof: A statistical mixture of the four possible isotopomeric oxazolines was formed, also indicating a rapid H/D scrambling of the starting materials 2b and 2b-d2.