331991-04-9Relevant articles and documents
Generation of ketenes from acid chlorides using NaH/crown ether shuttle-deprotonation for use in asymmetric catalysis.
Taggi, Andrew E,Wack, Harald,Hafez, Ahmed M,France, Stefan,Lectka, Thomas
, p. 627 - 629 (2002)
[reaction: see text] We describe methodology for the in situ generation of reactive monosubstituted ketenes from acid chlorides through a shuttle deprotonation process using NaH as an inexpensive stoichiometric base and a crown ether cocatalyst. We have s
Catalytic, Asymmetric α-Chlorination of Acid Halides
France, Stefan,Wack, Harald,Taggi, Andrew E.,Hafez, Ahmed M.,Wagerle, Ty R.,Shah, Meha H.,Dusich, Crystal L.,Lectka, Thomas
, p. 4245 - 4255 (2007/10/03)
We present a full account of a tandem catalytic, asymmetric chlorination/esterification process that produces highly optically enriched α-chloroesters from inexpensive, commercially available acid halides using cinchona alkaloid derivatives as catalysts and polychlorinated quinones as halogenating agents. We have performed kinetics and control experiments to investigate the reaction mechanism and establish conditions under which the reactions can be best performed. We have developed NaH and NaHCO3 shuttle base systems as the easiest and most cost-effective ways of conducting the reactions, rendering the methodology economically competitive with known chiral halogenation procedures. We have also demonstrated the utility of our reactions by converting the products to synthetically useful derivatives.