1027898-42-5

Basic information

• Product Name: {(1R,2R)-1-[Bis-(4-methoxy-phenyl)-phenyl-methoxymethyl]-2-chloro-1,5-dimethyl-hex-4-enyloxy}-triethyl-silane
• CAS NO: 1027898-42-5
• Molecular Weight: 609.321
• Mol File: 1027898-42-5.mol

Chemical Properties

• CAS DataBase Reference: {(1R,2R)-1-[Bis-(4-methoxy-phenyl)-phenyl-methoxymethyl]-2-chloro-1,5-dimethyl-hex-4-enyloxy}-triethyl-silane(CAS DataBase Reference)
• NIST Chemistry Reference: {(1R,2R)-1-[Bis-(4-methoxy-phenyl)-phenyl-methoxymethyl]-2-chloro-1,5-dimethyl-hex-4-enyloxy}-triethyl-silane(1027898-42-5)
• EPA Substance Registry System: {(1R,2R)-1-[Bis-(4-methoxy-phenyl)-phenyl-methoxymethyl]-2-chloro-1,5-dimethyl-hex-4-enyloxy}-triethyl-silane(1027898-42-5)

Safety Data

• Hazardous Substances Data: 1027898-42-5(Hazardous Substances Data)

Upstream product

• 204918-25-2 (Z)-2,6-dimethylhepta-2,5-dien-1-ol tetrahydropyranyl ether 
• 204918-27-4 (2R,3R)-3-chloro-2,6-dimethyl-5-heptene-1,2-diol 
• 204918-26-3 (2R,3S)-2-methyl-3-(3-methyl-2-butenyl)oxiranemethanol 
• 27312-92-1 (4-methylpent-3-en-1-yl)triphenylphosphonium bromide 
• 40615-36-9 4,4'-dimethoxytrityl chloride 
• 43160-59-4 (Z)-2,6-dimethyl-2,5-heptadien-1-ol 
• 2270-59-9 1-bromo-4-methylpent-3-ene 

Relevant articles and documents

Total Syntheses of the Cytotoxic Marine Natural Product, Aplysiapyranoid C

The first total syntheses of the cytotoxic marine natural product, aplysiapyranoid C, 1c, are reported. The Wittig reaction of 4-methyl-3-pentenyltriphenylphosphorane with the THP ether of hydroxy-acetone gave in 88% yield the Z-alkene 4 which was hydrolyzed to the alcohol 5 in 72% yield. Sharpless asymmetric epoxidation of 5 afforded the epoxy alcohol 6 in 91% yield and 81% ee. Opening of the epoxide of 6 with ammonium chloride in DMSO gave in 76% yield the chloro diol 7 which was converted to the primary TBS ether 8 in 95% yield. Opening of the epoxy alcohol 6 with HCl and Ti(OiPr)4 afforded the desired chloro diol 7 as the minor product along with the rearranged chloromethyl diol 9. This compound is presumably formed by opening of the protonated epoxide to give a butenyl cation which rearranges to the cyclopropylcarbinyl cation and is then trapped by chloride ion at the unsubstituted cyclopropyl carbon, regenerating the alkene. Cyclization of the TBS ether 8 with tetrabromocyclohexadienone (TBCO) afforded a mixture of all four possible cyclization products, the desired tetrahydropyrans 11a,b and the tetrahydrofurans 12a,b with the former being isolated in 70% yield. Hydrolysis of the TBS ether afforded the primary alcohols from which the desired isomer, 13, could be isolated (24% overall from 8). Swern oxidation furnished the aldehyde 14 which was subjected to the Takai chlorovinylation to give a mixture of aplysiapyranoid C 1c and the reduced product, dechloroaplysiapyranoid C 15. This dechlorination under these conditions is quite unusual. A second synthesis of aplysiapyranoid C avoided this problem. Selective protection of the more hindered tertiary alcohol of the chloro diol 7 afforded the primary alcohol 16 in which the tertiary alcohol was protected as the triethylsilyl ether. Swern oxidation, Takai reaction, and desilylation gave the dichloro alkenol 17 in 52% overall yield. In this case, only a small amount of the corresponding dechlorinated product was obtained. Final cyclization of 17 with TBCO afforded aplysiapyranoid C 1c as the major product in an isolated yield of 43%. Thus we have completed two total syntheses of aplysiapyranoid C 1c from the simple bromide 2 in eight or nine steps and good overall yield.