1407517-33-2

Upstream product

• 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 
• 1407517-32-1 (R,2E,4E)-6-(tert-butyldiphenylsilanyloxy)-6-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-4-methylhexa-2,4-dienol 
• 73346-74-4 (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dimethanol 
• 1407517-31-0 (R,2E,4E)-ethyl 6-(tert-butyldiphenylsilanyloxy)-6-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-4-methylhexa-2,4-dienoate 
• 1407517-30-9 (R,E)-4-(tert-butyldiphenylsilanyloxy)-4-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-2-methylbut-2-enal 
• 1407517-29-6 (R,E)-4-(tert-butyldiphenylsilanyloxy)-4-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-2-methylbut-2-en-1-ol 
• 1407517-28-5 (R,E)-ethyl 4-(tert-butyldiphenylsilanyloxy)-4-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-2-methylbut-2-enoate 
• 1407517-27-4 (S)-2-(tert-butyldiphenylsilanyloxy)-2-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)acetaldehyde 

Downstream Products

• 1407517-34-3 tert-butyl((1R,2E,4E,6R)-1-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-6-hydroxy-3-methylnona-2,4,8-trienyloxy)diphenylsilane 
• 1407517-35-4 tert-butyl((1R_.2E,4E,6R)-1-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-6-methoxy-3-methylnona-2,4,8-trienyloxy)diphenylsilane 
• 1407517-36-5 (3R,4E,6E,8R)-8-(tert-butyldiphenylsilanyloxy)-8-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-3-methoxy-6-methylocta-4,6-dienal 
• 1407517-37-6 ((1R,2E,4E,6R,8E)-9-bromo-1-((2R,4R,6R)-4,6-dimethoxytetrahydro-2H-pyran-2-yl)-6-methoxy-3-methylnona-2,4,8-trienyloxy)(tertbutyl)diphenylsilane 

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%.