Enantioselective total synthesis of erogorgiaene: applications of asymmetric Cu-catalyzed conjugate additions of alkylzincs to acyclic enones.
The first enantioselective synthesis of erogorgiaene (1), an inhibitor of mycobacterium tuberculosis, is disclosed. The total synthesis highlights the utility of asymmetric conjugate additions (ACA) of alkylzincs to acyclic alpha,beta-unsaturated ketones catalyzed by peptidic phosphine ligands and (CuOTf)(2).C(6)H(6). Moreover, several critical attributes of this catalytic C-C bond-forming reaction are illustrated in the context of the total synthesis; these include the significance of various structural features of the amino acid-based chiral ligands and the chiral ligand's effectiveness in reactions involving achiral and chiral substrates. In addition, the total synthesis showcases some of the special properties of nonphosphine Ru complex 3 as a highly effective catalyst for olefin cross-metathesis.
Cesati
Richard R
RR
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
de Armas
Judith
J
Hoveyda
Amir H
AH
D000475:Alkenes / Q000737:chemistry*; D002074:Butanones / Q000737:chemistry; D002384:Catalysis; D003300:Copper / Q000737:chemistry; D004224:Diterpenes / Q000138:chemical synthesis*; D007659:Ketones / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
D000475:Alkenes; D002074:Butanones; D004224:Diterpenes; D007659:Ketones; D009942:Organometallic Compounds; C428183:erogorgiaene; D003300:Copper; C057920:3-buten-2-one; D015032:Zinc