188557-64-4

Upstream product

• 188557-50-8 (1R,4S,4aS,5R,6S,8aR)-5-(tert-Butyl-dimethyl-silanyloxy)-1,2,3,4-tetrachloro-9,9-dimethoxy-6-methyl-8-trimethylsilanyloxy-1,4,4a,5,6,8a-hexahydro-1,4-methano-naphthalene 
• 188557-58-6 (+)-(1R,3R,5R,6S,7S,8S,9R,10S,11R,12R)-10,12-dibenzyloxy-3-ethoxy-6,11-dimethyl-2-oxatetracyclo[6.4.0.0^3,7.0^5,9]dodecan-6-ol 
• 188557-52-0 (1S,4R,4aR,5R,6R,7S,8R,8aS)-8-(tert-Butyl-dimethyl-silanyloxy)-1,2,3,4-tetrachloro-9,9-dimethoxy-7-methyl-1,4,4a,5,6,7,8,8a-octahydro-1,4-methano-naphthalene-5,6-diol 
• 188557-49-5 (1S,4R,4aR,8R,8aS)-8-(tert-Butyl-dimethyl-silanyloxy)-1,2,3,4-tetrachloro-9,9-dimethoxy-4,4a,8,8a-tetrahydro-1H-1,4-methano-naphthalen-5-one 
• 188557-63-3 (1S,4R,4aR,5S,8R,8aS)-8-(tert-Butyl-dimethyl-silanyloxy)-1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,5,8,8a-hexahydro-1,4-methano-naphthalen-5-ol 
• 188560-71-6 (+)-(1R,3R,5R,7R,8S,9R,10S,11R,12R)-3-ethoxy-6,6-dimethoxy-11-methyl-2-oxatetracyclo[6.4.0.0^3,7.0^5,9]dodecan-10,12-diol 
• 188557-48-4 (1S,2S,3R,6S,7R,8R)-1,8,9,10-Tetrachlor-11,11-dimethoxy-3-(dimethyl-t-butylsilyloxy)-6<<(1'R,2'S,4'S,6'S,7'R)-1',10',10'-trimethyl-3'-oxatricyclo<5.2.1.0^2',6'>dec-4'-yl>oxy>tricyclo<6.2.1.0^2,7>undeca-4,9-dien 
• 100-39-0 benzyl bromide 
• 101199-21-7 (meso)-(1R*,2R*,3S*,6R*,7S*,8S*)-1,8,9,10-Tetrachlor-11,11-dimethoxytricyclo<6.2.1.0^2,7>undeca-4,9-dien-3,6-diol 
• 188557-59-7 (4R,4aR,5S,6R,7R,8R,8aR)-4-Acetyl-5,7-bis-benzyloxy-8-hydroxy-6-methyl-octahydro-naphthalen-2-one 
• 188557-55-3 (+)-(1R,3R,5R,7R,8S,9R,10S,11R,12R)-10,12-dibenzyloxy-3-ethoxy-6,6-dimethoxy-11-methyl-2-oxatetracyclo[6.4.0.0^3,7.0^5,9]dodecane 
• 188557-56-4 (+)-(1R,3R,5R,7R,8S,9R,10S,11R,12R)-10,12-dibenzyloxy-3-ethoxy-11-methyl-2-oxatetracyclo[6.4.0.0^3,7.0^5,9]dodecan-6-one 
• 188557-51-9 (1S,4R,4aR,6R,7S,8R,8aS)-8-(tert-Butyl-dimethyl-silanyloxy)-1,2,3,4-tetrachloro-6-hydroxy-9,9-dimethoxy-7-methyl-4,4a,6,7,8,8a-hexahydro-1H-1,4-methano-naphthalen-5-one 

Relevant academic research and scientific papers

Approach towards an EPC synthesis of nodusmicin. Part 5: Stereoselective introduction of a side chain at the cis-decalin part of nodusmicin

The introduction of the side chain at C-4 of cis-decalin 2 and closure of the oxygen bridge are reported. Partial dehydrogenation of 2 was followed by oxymercuration and halogen-mercury exchange. Intermolecular radical addition to acrylic ester occurred from the convex face of the tricyclic compounds 7a and 7b. Consecutive epimerization failed. Therefore, two methods using intramolecular attachment of the side chain were developed. Formation of the β-iodoacetal of the cyclic allylic alcohol 21 permitted intramolecular radical addition generating the desired configuration at C-4 of the decalin. Likewise formation of the β bromoacetal with the exo-cyclic hydroxy group of tricycle 12 led via SN2-reaction to tetrahydropyrans with the desired configuration at C-4. The oxygen bridge was introduced by dehydration of the exo-cyclic alcohol and consecutive oxymercuration. Mercury-oxygen exchange completed the reaction sequence.

Approach towards an EPC synthesis of nodusmicin - III. Preparation of the oxygen bridged decalin part of nodusmicin

Starting with the unsaturated 1,4-mesa-diol 1, the enantiomerically pure 4-silyloxy enone 6 is prepared in high yields via diastereomeric acetals and equilibration. Enone 6 is converted to the cis-decalinone derivative 17 with fragmentation as the key step. Consequently oxidation to the conjugated enedione 24, reduction to the enediol 25 and intramolecular oxymercuration produces, depending on the reaction conditions, either the unsaturated tricyclic ether 27, which constitutes a link to a known 18-deoxynargenicin synthesis, or the saturated tricyclic ether 26, which represents the starting material for the construction of the tenmembered ring of nodusmicin.