148933-48-6

Upstream product

• 148933-47-5 ((E)-(S)-3-Methoxy-2-methyl-4-(R)-oxiranyl-but-1-enyl)-trimethyl-silane 
• 80522-42-5 triisopropylsilyl trifluoromethanesulfonate 
• 168777-77-3 1-Methoxy-4-((E)-(2R,5S,7S)-7-methoxy-2,8-dimethyl-5-triisopropylsilanyloxy-9-trimethylsilanyl-non-8-enyloxymethyl)-benzene 
• 168777-76-2 (E)-(3S,5S,8R)-3-Methoxy-9-(4-methoxy-benzyloxy)-2,8-dimethyl-1-trimethylsilanyl-non-1-en-5-ol 
• 148933-46-4 [(E)-(S)-4-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-3-methoxy-2-methyl-but-1-enyl]-trimethyl-silane 
• 148933-52-2 (E)-(S)-1-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-3-methyl-4-trimethylsilanyl-but-3-en-2-ol 
• 148933-45-3 (E)-1-((R)-2,2-Dimethyl-[1,3]dioxolan-4-yl)-3-methyl-4-trimethylsilanyl-but-3-en-2-one 

Downstream Products

• 148933-50-0 (4R,5S)-3-[(E)-(2R,3S,4R,7S,9S)-3-Hydroxy-11-iodo-9-methoxy-2-(4-methoxy-benzyloxy)-4,10-dimethyl-7-triisopropylsilanyloxy-undec-10-enoyl]-4-methyl-5-phenyl-oxazolidin-2-one 

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

A Highly Convergent Strategy Towards Rapamycin. Stereoselective Construction of the C8-C18 Fragment

A strategy for a total synthesis of the immunosuppressant agent rapamycin 1 is outlined and the stereoselective construction of a suitably functionalized C8-C18 fragment 2 is described.