920034-36-2

Upstream product

• 920018-78-6 (R,E)-4-(tert-butyldiphenylsilanyloxy)-4-((2R,4R,6S)-4-methoxy-6-(phenylthio)tetrahydro-2H-pyran-2-yl)-2-methylbut-2-en-1-ol 
• 18162-48-6 tert-butyldimethylsilyl chloride 
• 920018-57-1 (R)-4-((4R,5R)-5-((tert-butyldimethylsilanyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)-3-methoxybutanal 
• 920018-56-0 tert-butyl(((4R,5R)-5-((S)-2-methoxypent-4-enyl)-2,2-dimethyl-1,3-dioxolan-4-yl)methoxy)dimethylsilane 
• 191723-84-9 2-((4R,5R)-5-((tert-butyldimethylsilanyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)acetaldehyde 
• 920018-74-2 2-((4R,5R)-5-((tert-butyldimethylsilanyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)acetonitrile 
• 872831-91-9 ((4S,5R)-5-(((tert-butyl-dimethyl)silyl-oxy)-methyl)-2,2-dimethyl 1,3-dioxolan-4-yl) methanyl iodide 
• 191671-39-3 ((4R,5R)-5-((tert-butyldimethylsilyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)methanol 4-methylbenzenesulfonate 
• 145554-06-9 [(4R,5R)-5-({[tert-butyl(dimethyl)silyl]oxy}methyl)-2,2-dimethyl-1,3-dioxolan-4-yl]methanol 
• 920018-60-6 (R)-2-(tert-butyldiphenylsilanyloxy)-2-((2R,4R,6S)-4-methoxy-6-(phenylthio)tetrahydro-2H-pyran-2-yl)ethanol 
• 73346-74-4 (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dimethanol 
• 920018-76-4 (R)-2-(tert-butyldiphenylsilanyloxy)-2-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)ethanol 
• 920018-75-3 (R)-5-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-2,2,8,8,9,9-hexamethyl-3,3-diphenyl-4,7-dioxa-3,8-disiladecane 
• 920018-77-5 (S)-2-(tert-butyldiphenylsilanyloxy)-2-((2R,4R,6S)-4-methoxy-6-(phenylthio)tetrahydro-2H-pyran-2-yl)acetaldehyde 

Downstream Products

• 920034-29-3 2-(((2S,4R,6R)-6-((1R,2E,4E,6R,8E)-9-bromo-1-(tert-butyldiphenylsilanyloxy)-6-methoxy-3-methylnona-2,4,8-trienyl)-2,4-dimethoxytetrahydro-2Hpyran-2-yl)methyl)-4-((E)-2-((2R,3R,4S,5S,6R)-6-(2-(tert-butyldimethylsilanyloxy)ethyl)-4-(4-methoxybenzyloxy)-3,5-dimethyltetrahydro-2H-pyran-2-yl)prop-1-enyl)oxazole 
• 920034-27-1 (2S,4R,6R)-2-((4-((E)-2-((2R,3R,4S,5S,6R)-6-(2-(tert-butyldimethylsilanyloxy)ethyl)-4-(4-methoxybenzyloxy)-3,5-dimethyltetrahydro-2H-pyran-2-yl)prop-1-enyl)oxazol-2-yl)methyl)-6-((R,E)-2,2,7,10,10,11,11-heptamethyl-3,3-diphenyl-4,9-dioxa-3,10-disiladodec-6-en-5-yl)-4-methoxytetrahydro-2H-pyran-2-ol 
• 920034-41-9 2-((2R,3S,4S,5R,6R)-6-((E)-1-(2-(((2S,4R,6R)-6-((1R,2E,4E,6R,8E)-9-bromo-1-(tert-butyldiphenylsilanyloxy)-6-methoxy-3-methylnona-2,4,8-trienyl)-2,4-dimethoxytetrahydro-2H-pyran-2-yl)methyl)oxazol-4-yl)prop-1-en-2-yl)-4-(4-methoxybenzyloxy)-3,5-dimethyltetrahydro-2H-pyran-2-yl)ethanol 
• 920034-30-6 2-((2R,3S,4S,5R,6R)-6-((E)-1-(2-(((2S,4R,6R)-6-((1R,2E,4E,6R,8E)-9-bromo-1-(tert-butyldiphenylsilanyloxy)-6-methoxy-3-methylnona-2,4,8-trienyl)-2,4-dimethoxytetrahydro-2H-pyran-2-yl)methyl)oxazol-4-yl)prop-1-en-2-yl)-4-(4-methoxybenzyloxy)-3,5-dimethyltetrahydro-2H-pyran-2-yl)acetaldehyde 
• 920034-28-2 (R,E)-4-((2R,4R,6S)-6-((4-((E)-2-((2R,3R,4S,5S,6R)-6-(2-(tert-butyldimethylsilanyloxy)ethyl)-4-(4-methoxybenzyloxy)-3,5-dimethyltetrahydro-2Hpyran-2-yl)prop-1-enyl)oxazol-2-yl)methyl)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-4-(tert-butyldiphenylsilanyloxy)-2-methylbut-2-enal 
• 920034-39-5 (2S,4R,6R)-6-((R,E)-1-(tert-butyldiphenylsilanyloxy)-4-hydroxy-3-methylbut-2-enyl)-2-((4-((E)-2-((2R,3R,4S,5S,6R)-6-(2-hydroxyethyl)-4-(4-methoxybenzyloxy)-3,5-dimethyltetrahydro-2H-pyran-2-yl)prop-1-enyl)oxazol-2-yl)methyl)-4-methoxytetrahydro-2H-pyran-2-ol 
• 920034-40-8 (R,E)-4-(tert-butyldiphenylsilanyloxy)-4-((2R,4R,6S)-6-((4-((E)-2-((2R,3R,4S,5S,6R)-6-(2-hydroxyethyl)-4-(4-methoxybenzyloxy)-3,5-dimethyltetrahydro-2H-pyran-2-yl)prop-1-enyl)oxazol-2-yl)methyl)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-2-methylbut-2-enal 
• 920034-25-9 (4R,6R)-6-((R,E)-2,2,7,10,10,11,11-heptamethyl-3,3-diphenyl-4,9-dioxa-3,10-disiladodec-6-en-5-yl)-4-methoxy-tetrahydropyran-2-one 

Relevant academic research and scientific papers

Total synthesis of the marine toxin phorboxazole A using palladium(ii)-mediated intramolecular alkoxycarbonylation for tetrahydropyran synthesis

The potent antitumor agent phorboxazole A was synthesized from six subunits comprising C1-C2 (115), C3-C8 (98), C9-C19 (74), C20-C32 (52), C33-C41 (84) and C42-C46 (85). Tetrahydropyrans B and C containing cis-2,6-disubstitution were fabricated via palladium(ii)-mediated intramolecular alkoxycarbonylation which, in the case of tetrahydropyran C, was carried out with catalytic palladium(ii) and p-benzoquinone as the stoichiometric re-oxidant. Tetrahydropyran D was obtained by a stereoselective tin(iv)-catalyzed coupling of a C9 aldehyde with an allylsilane, and the C19-C20 connection was made using a completely stereoselective Wittig-Schlosser (E) olefination. Coupling of the oxazole C32 methyl substituent with the intact C33-C46 δ-lactone 3 was accompanied by elimination of the vinyl bromide to a terminal alkyne, but the C32-C33 linkage was implemented successfully with 83 and C33-C41 lactone 84. The C42-C46 segment of the side chain was then appended via Julia-Kocienski olefination. The macrolide portion of phorboxazole A was completed by means of an Ando-Still-Gennari intramolecular (Z)-selective olefination at C2-C3 which required placement of a (dimethoxyphosphinyl)acetate moiety at C24. Final deprotection led to phorboxazole A via a route in which the longest linear sequence is 37 steps and the overall yield is 0.36%.

Total synthesis of phorboxazole A. 2. Assembly of subunits and completion of the synthesis

(Chemical Equation Presented) Subunits of phorboxazole A containing C1-C2, C3-C8, C9-C19, C20-C32, C33-C41, and C42-C46 were connected in a sequence that first linked C32 with C33 and then C41 with C42. A C3-C8 fragment was joined to C9-C19, and the assem