211491-49-5

Upstream product

• 950598-33-1 (2E,6S,7Z,10R,11R,12S,14S)-6,10:14,15-diepoxy-11,12-isopropylidenedioxy-3,7,11,15-tetramethyl-1-(phenylthio)hexadeca-2,7-diene 
• 195819-75-1 (5S,6S,9R,10E,14E)-16-(2,2-dimethylpropanoyloxy)-9-hydroxy-5,6-(isopropylidenedioxy)-2,6,10,14-tetramethyl-2,10,14-hexadecatrien-7-one 
• 195819-76-2 (5S,6R,7R,9S,10E,14E)-16-(2,2-dimethylpropanoyloxy)-5,6-(isopropylidenedioxy)-2,6,10,14-tetramethyl-2,10,14-hexadecatriene-7,9-diol 
• 195819-82-0 (2E,6S,10R,11R,12S)-1-(2,2-dimethylpropanoyloxy)-6,10-epoxy-11,12-(isopropylidenedioxy)-3,7,11,15-tetramethyl-2,14-hexadecadien-8-one 
• 195819-84-2 2,2-Dimethyl-propionic acid (E)-3-methyl-5-{(2S,6R)-3-methyl-4-trifluoromethanesulfonyloxy-6-[(4R,5S)-2,2,4-trimethyl-5-(3-methyl-but-2-enyl)-[1,3]dioxolan-4-yl]-5,6-dihydro-2H-pyran-2-yl}-pent-2-enyl ester 
• 195819-86-4 2,2-Dimethyl-propionic acid (E)-5-{(2S,6R)-6-[(4R,5S)-5-(3,3-dimethyl-oxiranylmethyl)-2,2,4-trimethyl-[1,3]dioxolan-4-yl]-3-methyl-5,6-dihydro-2H-pyran-2-yl}-3-methyl-pent-2-enyl ester 
• 195819-81-9 (2E,6E,10R,11R,12S)-1-(2,2-dimethylpropanoyloxy)-10-hydroxy-11,12-(isopropylidenedioxy)-3,7,11,15-tetramethyl-2,6,14-hexadecatrien-8-one 
• 195819-85-3 (2E,6S,7Z,10R,11R,12S)-1-(2,2-dimethylpropanoyloxy)-6,10-epoxy-11,12-(isopropylidenedioxy)-3,7,11,15-tetramethyl-2,7,14-hexadecatriene 
• 211491-58-6 Acetic acid (R)-1-[(4R,5S)-2,2,4-trimethyl-5-(3-methyl-but-2-enyl)-[1,3]dioxolan-4-yl]-ethyl ester 
• 195819-72-8 (3S,4S)-3,4-(isopropylidenedioxy)-3,7-dimethyl-6-octen-2-one 
• 195819-73-9 (2E,6E)-2,6-dimethyl-8-(2,2-dimethylpropanoyloxy)-2,6-octadienal 
• 211491-59-7 (R)-1-[(4R,5S)-2,2,4-Trimethyl-5-(3-methyl-but-2-enyl)-[1,3]dioxolan-4-yl]-ethanol 
• 211491-56-4 Acetic acid (S)-1-((S)-1-hydroxy-1-methyl-2-oxo-propyl)-4-methyl-pent-3-enyl ester 
• 195819-70-6 (2R,3R,4S)-2-acetoxy-3,7-dimethyl-6-octene-3,4-diol 

Relevant academic research and scientific papers

Total synthesis of methyl sarcophytoate, a marine natural biscembranoid

(Chemical Equation Presented) The total synthesis of methyl sarcophytoate (1), a marine natural biscembranoid, has been achieved by the thermal Diels-Alder reaction between the 14-membered dienophile unit, methyl sarcoate (2), and the 14-membered diene unit 64. Methyl sarcoate (2) was prepared using n-BuLi-Bu2Mg-mediated dithiane coupling, Kosugi-Migita-Stille coupling, and Grubbs ring-closing metathesis. The diene unit 64 was prepared using Sharpless asymmetric epoxidation, Grubbs ring-closing metathesis, 6-exo-tet epoxide opening, and n-BuLi-Bu2Mg-mediated Ito-Kodama cyclization. The final Diels-Alder reaction between 2 and 64 proceeded with high site, endo/exo, π-face, and regioselectivities. During this reaction, partial E → Z isomerization at the C4 position was observed.

Synthetic Studies on Biscembranoids. Asymmetric Total Synthesis of the 14-Membered Diene Unit of Methyl Sarcophytoate

An asymmetric total synthesis of the 14-membered diene unit, (1S,2S,4E,6E,10S,11Z,14R)-10,14-epoxy-4-isopropenyl-1,7,11-trimethyl-4,6,11- cyclotetradecatnene-1,2-diol (3), of methyl sarcophytoate (1) has been achieved. Methyl ketone, (3S,4S)-3,4-(isopropylidenedioxy)-3,7-dimethyl-6-octen-2-one (6), was enantioselectively prepared from geraniol via Sharpless asymmetric epoxidation and a regioselective epoxide-opening reaction. The aldol coupling between the lithium enolate of 6 and aldehyde, (2E,6E)-2,6-dimethyl-8-(2,2-dimethylpropanoyloxy)-2,6-octadienal (7), which was also prepared from geraniol, gave a 1 : 1 separable mixture of the adducts (17 and 18). Reduction of the carbonyl group in 17 and 18, followed by regioselective oxidation of the allylic hydroxy group, afforded α,β-unsaturated ketone, (2E, 6E,10R,11R,12S)-1-(2,2-dimethylpropanoyloxy)-10-hydroxy-11,12- (isopropylidenedioxy)-3,7,1,15-tetramethyl-2,6,14-hexadecatrien-8-one (5). The intramolecular oxy-Michael addition of 5 followed by regioselective enol inflation and deoxygenation gave dihydropyran, (2E,6S,7Z,10R,11R,12S)-1-(2,2-dimethylpropanoyloxy)-6,10-epoxy-11,12-(isopropyl- idenedioxy)-3,7,11,15-tetramethyl-2,7,14-hexadecatriene (31). The regioselective epoxidation of 31 and a subsequent functional-group transformation gave (2E,6S,7Z,10R,11R,12S,4RS)-6,10:14,15-diepoxy-11,12-(isopropylidenedioxy)-3, 7,11,15-tetramethyl-1-(phenylthio)-2,7-hexadecadiene (4). The 14-membered ring formation was achieved by the treatment of 4 with the n-BuLi-Bu2Mg complex to give (1Z,3S,6E,8RS,9RS,11S,12R,13R)-3,13-epoxy-9-(1-hydroxy-1-methylethyl)-11,12- (isopropylidenedioxy)-2,6,12-trimethyl-8-(phenylthio)-1,6-cyclotetradecadiene (33), which was transformed to 3 through triene construction and deacetonidation.