220213-63-8

Upstream product

• 220213-54-7 (E)-(R)-5-(4-Methoxy-benzyloxy)-2,4-dimethyl-pent-2-en-1-ol 
• 220213-53-6 (S)-5-(4-Methoxy-benzyloxy)-2,4-dimethyl-pent-1-en-3-ol 
• 132969-60-9 (2S)-3-[(4-methoxybenzyl)oxy]-2-methylpropanal 
• 123558-64-5 N-(4-methoxybenzyl)-2,2,2-trichloroacetamide 
• 136320-64-4 (2R)-3-[(4-methoxybenzyl)oxy]-2-methylpropanol 
• 132969-71-2 methyl (2S)-[(4-methoxybenzyl)oxy]-2-methylpropanoate 

Downstream Products

• 220213-55-8 (2S,3R)-3-[(S)-2-(4-Methoxy-benzyloxy)-1-methyl-ethyl]-2-methyl-oxirane-2-carbaldehyde 
• 236117-59-2 (R)-2-((S)-(tert-Butyl-dimethyl-silanyloxy)-{(2S,3R)-3-[(S)-2-(4-methoxy-benzyloxy)-1-methyl-ethyl]-2-methyl-oxiranyl}-methyl)-but-3-en-1-ol 
• 236117-56-9 Acetic acid (2S,3S,4S)-2-((S)-(tert-butyl-dimethyl-silanyloxy)-{(2S,3R)-3-[(S)-2-(4-methoxy-benzyloxy)-1-methyl-ethyl]-2-methyl-oxiranyl}-methyl)-4-methyl-5-oxo-3-triethylsilanyloxy-pentyl ester 
• 462656-83-3 C₂₅H₃₅NO₇ 
• 236117-60-5 C₃₀H₅₀O₇Si 
• 462656-85-5 C₂₆H₄₂O₇Si 
• 462656-84-4 C₂₇H₄₄O₆Si 
• 462656-94-6 C₃₁H₄₉NO₇Si 
• 236117-62-7 Acetic acid (2S,3R,4R,5S)-2-((S)-(tert-butyl-dimethyl-silanyloxy)-{(2S,3R)-3-[(S)-2-(4-methoxy-benzyloxy)-1-methyl-ethyl]-2-methyl-oxiranyl}-methyl)-5-hydroxy-4,8-dimethyl-7-oxo-3-triethylsilanyloxy-nonyl ester 

Relevant academic research and scientific papers

Total syntheses of (+)-tedanolide and (+)-13-deoxytedanolide

Convergent total syntheses of the potent cytotoxins (+)-tedanolide (1) and (+)-13-deoxytedanolide (2) are described. The carbon framework of these compounds was assembled via a stereoselective aldol reaction that unifies the C(1)-C(12) ketone fragment 5 with a C(13)-C(23) aldehyde fragment 6 (for 13-deoxytedanolide) or 52 (for tedanolide). Multiple obstacles were encountered en route to (+)-1 and (+)-2 that required very careful selection and orchestration of the stereochemistry and functionality of key intermediates. Chief among these issues was the remarkable stability and lack of reactivity of hemiketals 33b and 34 that prevented the tedanolide synthesis from being completed from aldol 4. Key to the successful completion of the tedanolide synthesis was the observation that the 13-deoxy hemiketal 36 could be oxidized to C(11, 15)-diketone 38 en route to 13-deoxytedanolide. This led to the decision to pursue the tedanolide synthesis via C(15)-(S)-epimers, since this stereochemical change would destabilize the hemiketal that plagued the attempted synthesis of tedanolide via C(15)-(R) intermediates. However, use of C(15)-(S)-configured intermediates required that the side-chain epoxide be introduced very late in the synthesis, owing to the ease with which the C(15)-(S)-OH cyclized onto the epoxide of intermediate 50.

Studies on the synthesis of tedanolide: synthesis of the C(5)-C(21) segment via a highly stereoselective fragment assembly aldol reaction of a chiral beta,gamma-unsaturated methyl ketone.

[formula: see text] A highly diastereoselective synthesis of 3, corresponding to the C(5)-C(21) segment of tedanolide, has been accomplished by a route utilizing the aldol reaction of aldehyde 4 and the beta,gamma-unsaturated methyl ketone 5.

A divergent approach to the myriaporones and tedanolide: Enantioselective preparation of the common intermediate

The tedanolide and myriaporone classes of natural products represent interesting targets for synthesis because of their structural similarity and biological activity. The asymmetric preparation of a potential common intermediate in the total synthesis of each of these targets is presented. The key step, a Zr-mediated allylation, allows for the efficient preparation of the hydroxypropionate structural unit.