Nicholas reactions with carboxylic acids for the synthesis of macrocyclic diolides.
[reaction: see text] We have developed a new strategy for the preparation of diolides using a cascade of Nicholas reactions. The carboxylic acid nucleophiles in these reactions are virtually unstudied participants in transformations of this type. Using this methodology, a 16-membered cobalt-complexed cyclic diyne is available in 28% yield over eight steps (an average of 85% per step). We can also easily access the uncomplexed diolide in one additional step.
Shea
Kevin M
KM
Department of Chemistry, Smith College, Northampton, Massachusetts 01063, USA. kshea@email.smith.edu
Closser
Kristina D
KD
Quintal
Miriam M
MM
D002264:Carboxylic Acids / Q000737:chemistry*; D003500:Cyclization; D006859:Hydrogen / Q000737:chemistry; D007783:Lactones / Q000737:chemistry; D015394:Molecular Structure; D012717:Sesquiterpenes / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
D002264:Carboxylic Acids; D007783:Lactones; D012717:Sesquiterpenes; D006859:Hydrogen