10.1021/ja055301t.s001 Akiyoshi Kuramochi Akiyoshi Kuramochi Hiroyuki Usuda Hiroyuki Usuda Kenzo Yamatsugu Kenzo Yamatsugu Motomu Kanai Motomu Kanai Masakatsu Shibasaki Masakatsu Shibasaki Total Synthesis of (±)-Garsubellin A American Chemical Society 2005 enantioselectivity Koga Claisen stereoselective aldol reaction prenyl stereoelective cyclohexenone neurotrophic compound sterically choline allyl group enantioselective alkylation synthesis ee Garsubellin formation oxidative acetaldehyde enantioenriched Total Synthesis garsubellin rearrangement metathesi 2005-10-19 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Total_Synthesis_of_Garsubellin_A/3262234 The first total synthesis of garsubellin A, a neurotrophic compound with potent choline acetyltransferase-inducing activity, is described. Keys for success were (1) stereoselective intermolecular aldol reaction at the C-4 position with acetaldehyde, (2) stereoelective Claisen rearrangement to introduce an allyl group to the most sterically crowded position at C-6, (3) ring-closing metathesis to construct the B-ring, and (4) Wacker-type oxidative C-ring formation. This synthetic route can be extended to an asymmetric synthesis of garsubellin A using the Koga catalytic enantioselective alkylation, which produced enantioenriched α-prenyl cyclohexenone with excellent enantioselectivity (95% ee).