195819-87-5

Upstream product

• 930-69-8 sodium thiophenolate 
• 108-98-5 thiophenol 
• 106-24-1 Geraniol 
• 37905-02-5 (2E,6E)-3,7-dimethyl-8-oxoocta-2,6-dien-1-yl acetate 
• 38290-51-6 (2E,6E)-8-hydroxy-2,6-dimethylocta-2,6-dienal 
• 50727-94-1 (2R,3R)-3-methyl-3-(4-methyl-3-pentenyl)oxiranemethanol 
• 195819-64-8 (R)-1-[(2R,3R)-2-Methyl-3-(3-methyl-but-2-enyl)-oxiranyl]-ethanol 
• 211491-57-5 (3S,4S)-3,4-Dihydroxy-3,7-dimethyl-oct-6-en-2-one 
• 195819-68-2 (2R,3R,4S)-4-acetoxy-3,7-dimethyl-6-octene-2,3-diol 
• 195819-70-6 (2R,3R,4S)-2-acetoxy-3,7-dimethyl-6-octene-3,4-diol 
• 211491-56-4 Acetic acid (S)-1-((S)-1-hydroxy-1-methyl-2-oxo-propyl)-4-methyl-pent-3-enyl ester 
• 211491-59-7 (R)-1-[(4R,5S)-2,2,4-Trimethyl-5-(3-methyl-but-2-enyl)-[1,3]dioxolan-4-yl]-ethanol 
• 195819-73-9 (2E,6E)-2,6-dimethyl-8-(2,2-dimethylpropanoyloxy)-2,6-octadienal 
• 195819-72-8 (3S,4S)-3,4-(isopropylidenedioxy)-3,7-dimethyl-6-octen-2-one 

Downstream Products

• 211491-49-5 (1Z,3S,6E,8S,9R,11S,12R,13R)-3,13-epoxy-9-(1-hydroxy-1-methylethyl)-11,12-(isopropylidenedioxy)-2,6,12-trimethyl-8-(phenylthio)-1,6-cyclotetradecadiene 
• 211491-51-9 (1Z,3S,6E,8R,9S,11S,12R,13R)-3,13-epoxy-9-(1-hydroxy-1-methylethyl)-11,12-(isopropylidenedioxy)-2,6,12-trimethyl-8-(phenylthio)-1,6-cyclotetradecadiene 

Relevant academic research and scientific papers

Enantiospecific Synthesis of the 14-Membered Diene Unit of Methyl Sarcophytoate

The enantiospecific synthesis of the 14-membered diene unit of methyl sarcophytoate has been achieved by using the Sharpless asymmetric epoxidation, the aldol reaction, the oxy-Michael addition, and the modified Ito-Kodama cyclization as the key steps. All the carbon skeleton was derived from geraniol only.

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.