Catalytic asymmetric assembly of stereodefined propionate units: an enantioselective total synthesis of (-)-pironetin.
Double diastereoselection in alkaloid-catalyzed acyl halide-aldehyde cyclocondensation (AAC) reactions provides a strategy for realizing syn- or anti-selective propionate aldol additions from a common reaction manifold. Matched AAC homologation of enantioenriched aldehydes afford cis-disubstituted beta-lactones as surrogates for syn aldols; the mismatched AAC reactions provide anti-selective aldols in the form of trans-disubstituted 2-oxetanones. The utility of this reaction technology in synthesis activities is exemplified in a catalytic asymmetric total synthesis of (-)-pironetin.
Shen
Xiaoqiang
X
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
Wasmuth
Andrew S
AS
Zhao
Junping
J
Zhu
Cheng
C
Nelson
Scott G
SG
D000970:Antineoplastic Agents / Q000138:chemical synthesis*; D002384:Catalysis; D007166:Immunosuppressive Agents / Q000138:chemical synthesis*; D008956:Models, Chemical; D011422:Propionates / Q000737:chemistry*; D011753:Pyrones / Q000138:chemical synthesis*; D013237:Stereoisomerism
D000970:Antineoplastic Agents; D007166:Immunosuppressive Agents; D011422:Propionates; D011753:Pyrones; C088446:pironetin