Intramolecular alkynylogous mukaiyama aldol reaction starting from bicyclic alkanones tethered to alkynyl esters: formal total synthesis of (+/-)-hamigeran B.
tert-Butyldimethylsilyltriflate (TBSOTf)/NEt(3) treatment of alkynyl esters tethered to bicycloalkanones led to tricyclic allenoates with total diastereoselectivity for the ring junction. The allenoates result from an intramolecular alkynylogous Mukaiyama aldol reaction promoted by a TBSOTf/NEt(3) dual activation, with key intermediates of silylalkynylketene acetals. This novel methodology was illustrated by a formal total synthesis of (+/-)-hamigeran B.
Miesch
Laurence
L
Université de Strasbourg, Institut de Chimie, UMR 7177 CNRS/ULP, Laboratoire de Chimie Organique Synthétique, 1 rue Blaise Pascal, BP 296/R8, 67008 Strasbourg Cedex, France.
Welsch
Tania
T
Rietsch
Vincent
V
Miesch
Michel
M
D000447:Aldehydes / Q000737:chemistry; D000466:Alkadienes / Q000737:chemistry; D000818:Animals; D018360:Crystallography, X-Ray; D004952:Esters; D008968:Molecular Conformation; D015394:Molecular Structure; D009285:Naphthoquinones / Q000138:chemical synthesis* / Q000737:chemistry; D011161:Porifera / Q000737:chemistry; D013237:Stereoisomerism
D000447:Aldehydes; D000466:Alkadienes; D004952:Esters; D009285:Naphthoquinones; C483756:hamigeran B; C025947:propadiene; C116609:3-hydroxybutanal