168960-76-7

Upstream product

• 148933-61-3 (4R,5S)-3-{(2R,4S)-2-[(1R,2R)-3-(tert-Butyl-diphenyl-silanyloxy)-1-hydroxy-2-methoxy-propyl]-4-methyl-hex-5-enoyl}-4-methyl-5-phenyl-oxazolidin-2-one 
• 148933-78-2 Toluene-4-sulfonic acid (2S,4S)-2-[(1R,2R)-3-(tert-butyl-diphenyl-silanyloxy)-1-hydroxy-2-methoxy-propyl]-4-methyl-hex-5-enyl ester 
• 148933-77-1 (2S,3R,4R)-5-(tert-Butyl-diphenyl-silanyloxy)-4-methoxy-2-((S)-2-methyl-but-3-enyl)-pentane-1,3-diol 
• 148933-62-4 (2R,3R,4R,6S)-1-(tert-Butyl-diphenyl-silanyloxy)-2-methoxy-4,6-dimethyl-oct-7-en-3-ol 
• 148933-82-8 tert-Butyl-[(3S,4R)-6,6-dibromo-3-(4-methoxy-benzyloxy)-4-methyl-hex-5-enyloxy]-dimethyl-silane 
• 148933-65-7 tert-Butyl-[(3S,4R)-3-(4-methoxy-benzyloxy)-4-methyl-hept-5-ynyloxy]-dimethyl-silane 
• 148933-59-9 (4R,5S)-4-Methyl-3-((S)-4-methyl-hex-5-enoyl)-5-phenyl-oxazolidin-2-one 
• 148933-81-7 (2S,3S)-5-(tert-Butyl-dimethyl-silanyloxy)-3-(4-methoxy-benzyloxy)-2-methyl-pentanal 
• 148933-64-6 tert-Butyl-[(3S,4R)-3-(4-methoxy-benzyloxy)-4-methyl-hex-5-enyloxy]-dimethyl-silane 
• 148933-80-6 (2R,3R,4R,6S)-2-Methoxy-3-(4-methoxy-benzyloxy)-4,6-dimethyl-oct-7-en-1-ol 
• 148933-79-3 (2R,3R,4R,6S)-2-Methoxy-4,6-dimethyl-oct-7-ene-1,3-diol 
• 168777-81-9 (3S,4R)-1-[(tert-butyldimethylsilyl)oxy]-4-methylhex-5-en-3-ol 
• 89922-82-7 3-(tert-butyldimethylsilanyloxy)propionaldehyde 
• 69274-86-8 (S)-(+)-4-methylhex-5-enoic acid 

Downstream Products

• 168777-88-6 C₆₅H₁₀₈INO₁₀Si₂ 
• 148933-76-0 C₈₁H₁₂₄INO₁₂Si₂ 
• 148933-74-8 C₈₀H₁₁₅NO₁₂Si₂ 
• 148933-91-9 C₈₀H₁₂₃NO₁₃Si₂ 
• 148933-90-8 C₈₁H₁₂₅NO₁₂Si₂ 
• 168777-87-5 C₇₇H₁₁₄O₁₂SSi₂ 
• 148933-55-5 C₇₂H₁₂₈INO₈Si₄ 
• 168777-86-4 (E)-(2S,3S,5S,6R,9R,10S,11R,12R,14S)-2-[(1S,3R,4R)-4-(tert-Butyl-diphenyl-silanyloxy)-3-methoxy-cyclohexylmethyl]-10-methoxy-5,11-bis-(4-methoxy-benzyloxy)-6,8,12,14-tetramethyl-9-triisopropylsilanyloxy-hexadeca-7,15-diene-1,3-diol 
• 148933-75-9 (E)-(2R,3S,5S,6R,9R,10S,11R,12R,14S)-1-[(1S,3R,4R)-4-(tert-Butyl-diphenyl-silanyloxy)-3-methoxy-cyclohexyl]-10-methoxy-5,11-bis-(4-methoxy-benzyloxy)-2,6,8,12,14-pentamethyl-9-triisopropylsilanyloxy-hexadeca-7,15-dien-3-ol 
• 148933-86-2 C₅₀H₈₆O₇Si₂ 
• 148933-87-3 (E)-(3S,4R,7R,8S,9R,10R,12S)-8-Methoxy-3,9-bis-(4-methoxy-benzyloxy)-4,6,10,12-tetramethyl-7-triisopropylsilanyloxy-tetradeca-5,13-dien-1-ol 
• 148933-73-7 (E)-(3S,4R,7R,8S,9R,10R,12S)-8-Methoxy-3,9-bis-(4-methoxy-benzyloxy)-4,6,10,12-tetramethyl-7-triisopropylsilanyloxy-tetradeca-5,13-dienal 
• 148933-72-6 (E)-(3S,4R,7R,8R,9R,10R,12S)-1-(tert-Butyl-dimethyl-silanyloxy)-8-methoxy-3,9-bis-(4-methoxy-benzyloxy)-4,6,10,12-tetramethyl-tetradeca-5,13-dien-7-ol 

Relevant academic research and scientific papers

Total Synthesis of Rapamycin

Details of the total synthesis of rapamycin (1) are reported.The synthesis required the preparation of intermediates 4-9 in nonracemic form; key coupling reactions included a chromium-mediated addition of vinyl iodide 8 to aldehyde 7 and an Evans aldol reaction to couple fragments 62 and 9.Intermediates 4 and 6 were joined through an amide bond formation to afford advanced intermediate 71.Swern oxidation of the diol in 71 was followed by a selective removal of the TES groups and a second Swern oxidation.Finally, removal of the remaining silyl protecting groups provided fully deprotected, penultimate intermediate 2 in which all carbons were in their proper oxidation state.Macrocyclization was achived through a tandem inter/intramolecular palladium-mediated Stille coupling reaction between distannylethene 3 and bis(vinyl iodide) 2.This latter process accomplished in one step the installation of the remaining two carbons of the natural product and the completion of its total synthesis. - Keywords: rapamycin, stannylethenes, Stille coupling, vinyl iodides