66335-71-5

Upstream product

• 206660-79-9 (S)-4-methyl-1-(trityloxy)pent-4-en-2-ol 
• 129940-50-7 (S)-tritylglycidol 
• 76-83-5 trityl chloride 
• 302554-87-6 (S)-2-allyloxy-4-methyl-1-trityloxy-4-pentene 

Downstream Products

• 410095-21-5 (S)-2-[(E)-(3S,4R)-8-(tert-Butyl-diphenyl-silanyloxy)-4-(4-methoxy-benzyloxy)-3-triisopropylsilanyloxy-oct-1-en-6-ynyl]-4-methyl-3,6-dihydro-2H-pyran 
• 410095-26-0 {(2S,3S)-3-[(E)-(2R,3S)-2-(4-Methoxy-benzyloxy)-5-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)-3-triisopropylsilanyloxy-pent-4-enyl]-oxiranyl}-methanol 
• 410095-25-9 (E)-(5R,6S)-5-(4-Methoxy-benzyloxy)-8-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)-6-triisopropylsilanyloxy-oct-7-en-2-yn-1-ol 
• 410095-22-6 (2E,7E)-(5R,6S)-5-(4-Methoxy-benzyloxy)-8-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)-6-triisopropylsilanyloxy-octa-2,7-dien-1-ol 
• 410095-20-4 5-(6-methyl-3,7-dioxa-bicyclo[4.1.0]hept-4-ylmethanesulfonyl)-1-phenyl-1H-tetrazole 
• 410095-15-7 (S)-5-[(4-methyl-3,6-dihydro-2H-pyran-2-yl)methylsulfonyl]-1-phenyl-1H-tetrazole 
• 410095-19-1 5-(4-methyl-3,6-dihydro-2H-pyran-2-ylmethylsulfanyl)-1-phenyl-1H-tetrazole 
• 527742-86-5 ((2S,3S)-3-{(2R,3R,4E)-2-(tert-butyldiphenylsilyloxy)-3-(methoxymethoxy)-5-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]pent-4-enyl}oxiran-2-yl)-1-(tert-butyldimethylsilyloxy)methane 
• 445306-64-9 4-[1-[2-(3-{6-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-3,6-dihydro-2H-pyran-2-yl}-2-methyl-propyl)-allyl]-5-(tert-butyl-diphenyl-silanyloxy)-6-methoxymethoxy-8-(4-methyl-3,6-dihydro-2H-pyran-2-yl)-octa-2,7-dienyloxy]-pentan-2-one 
• 445306-63-8 4-[1-[2-(3-{6-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-3,6-dihydro-2H-pyran-2-yl}-2-methyl-propyl)-allyl]-5-(tert-butyl-diphenyl-silanyloxy)-6-methoxymethoxy-8-(4-methyl-3,6-dihydro-2H-pyran-2-yl)-octa-2,7-dienyloxy]-pentan-2-ol 
• 445306-66-1 C₅₄H₈₄O₈Si₂ 
• 445306-65-0 2-(3-{6-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-3,6-dihydro-2H-pyran-2-yl}-2-methyl-propyl)-8-(tert-butyl-diphenyl-silanyloxy)-9-methoxymethoxy-11-(4-methyl-3,6-dihydro-2H-pyran-2-yl)-undeca-1,5,10-trien-4-ol 
• 527743-02-8 (S)-2-[(E)-(3S,4S)-4-(tert-Butyl-diphenyl-silanyloxy)-3-methoxymethoxy-6-triethylsilanyloxy-hex-1-enyl]-4-methyl-3,6-dihydro-2H-pyran 
• 445306-59-2 (1E,3S,4S)-4-(tert-butyldiphenylsilanyloxy)-1-[(2S)-4-methyl-3,6-dihydro-2H-pyran-2-yl]-6-(triethylsilanyloxy)-hex-1-en-3-ol 

Relevant academic research and scientific papers

Total synthesis of the microtubule stabilizing antitumor agent laulimalide and some nonnatural analogues: The power of sharpless' asymmetric epoxidation

Three different routes are described for the synthesis of deoxylaulimalide (3), which is the immediate precursor of the marine sponge metabolite laulimalide (1). These routes mainly differ with respect to their ring closing step. Thus, route 1 uses a Still-Gennari olefination, route 2 a Yamaguchi lactonization, and route 3 an intramolecular allylsilane-aldehyde addition for establishing the macrocyclic structure. The unprotected deoxy derivative 3 was subjected to Sharpless' asymmetric epoxidation (SAE). With (R,R)-tartrate the 16,17-epoxide laulimalide (1) is formed selectively, whereas (S,S)-tartrate generates the 21,22-epoxide 142. This demonstrates the high reagent control involved in the SAE process, which in this case is used to achieve high stereo- and regioselectivity. Laulimalide and some derivatives thereof have been tested with respect to antitumor activity and compared to standard compounds paclitaxel and epothilone B.

An improved synthesis of the C15-C28 fragment of laulimalide

The C15-C28 fragment of the paclitaxel-like antimicrotubule agent laulimalide has been synthesized in 12 linear steps from known epoxide 5, with an overall yield of 16%. The methyldihydropyran ring of the side chain was efficiently prepared using ring-closing olefin metathesis chemistry. The 19,20-diol stereochemistry originates in starting material 7 and the side chain was appended using a Kocienski-modified Julia coupling.