117897-41-3

Upstream product

• 108-98-5 thiophenol 
• 117897-40-2 (3'α,3'aα,7'β(E),7'aα)-(+/-)-ethyl 3-[3'-ethoxyoctahydro-7'a-(methoxymethyl)-2',5,5-trimethyl-1'-oxospiro[1,3-dioxane-2,5'-[5H]isoindol]-7'-yl]-2-propenoate 
• 117897-39-9 (3'α,3'a,α,7'β,7'a,α)-(+/-)-3'-ethoxy7'-formylhexahydro-7'a-(methoxymethyl)-2',5,5-trimethylspiro(1,3-dioxane-2,5'-[5H]isoindol)-1'-(4'H)-one 
• 117897-38-8 (3'α,3'aα,7'β,7'a,α)-(+/-)-7'-ethenyl-3'-ethoxyhexahydro-7'a-(methoxymethyl)-2',5,5-trimethylspiro(1,3-dioxane-2,5'-[5H]isoindol)-1'-(4'H)-one 
• 117897-37-7 (3'α,3'aα,7'β,7'a,α)-(+/-)-7'-ethenyl-3'-ethoxytetrahydro-2',5,5-trimethylspiro(1,3-dioxane-2,5'-[5H]isoindol)-1'-(4'H)-one 
• 117897-35-5 (3'aα,7'β,7'aα)-(+/-)-7'-(2-hydroxyethyl)tetrahydro-2',5,5-trimethylspiro(1,3-dioxane-2,5'-[5H]isoindole)-1',3'-(2'H,4'H)-dione 
• 117897-36-6 (3'aα,7'β,7'aα)-(+/-)-7'-ethenyltetrahydro-2',5,5-trimethylspiro(1,3-dioxane-2,5'-[5H]isoindole)-1',3'(2'H,4'H)-dione 
• 117897-33-3 2-({5-[(trimethylsilyl)oxy]-3(E),5-hexadienyl}oxy)tetrahydropyran 
• 117897-32-2 2-[(5-oxo-3(E)-hexenyl)oxy]tetrahydropyran 
• 117897-40-2 C₂₃H₃₇NO₇ 

Downstream Products

• 117897-44-6 (1α,3aα,4β(E),7'aα)-(+/-)-ethyl 3-isoindol-4-yl>-2-propenoate 

Relevant academic research and scientific papers

Free radical cyclizations in alkaloid total synthesis: (±)-21- oxogelsemine and (±)-gelsemine

Total syntheses of (±)-21-oxogelsemine (3) and (±)-gelsemine (1) are described. Free radical cyclizations play important roles in constructing the tricyclic core (40 → 41) and oxindole (93 → 96) substructures of the target alkaloids, and an isomerization-cyclization strategy (101 → 102) was used to complete construction of the gelsemine cage. Observations made along the way include intramolecular 1,4- and 1,6-hydrogen atom transfers (64 → 65 and 40 → 47) and a free radical cyclization-fragmentation sequence (85 → 86 + 87). A retroaldol-aldol strategy for adjusting oxindole stereochemistry in gelsemine-like structures is also described (72 → 74 and 86 → 87).

α-Acylamino Radical Cyclizations: Application to the Synthesis of a Tetracyclic Substructure of Gelsemine

Syntheses of gelsemine substructures 2 and 3 are described.Free-radical precursors 14,18,35 and 38 were prepared, and their behavior upon treatment with tri-n-butyltin hydride and AIBN was examined.The radical derived from 14 afforded reduction product 15, whereas the radicals derived from 18,35, and 38 gave cyclization products 23,37, and 39, respectively.Aspects of these free-radical cyclizations as well as the conversion of 23 and 37 to 2 and 3, respectively, are presented.