349539-76-0

Upstream product

• 90865-70-6 [3R]-4-Benzyloxy-3-methylbutanal 
• 289472-94-2 (2S)-2-(2-allyloxy-4-methyl-pent-4-enyloxy)-tetrahydropyran 
• 273733-89-4 (4S,6R)-7-(benzyloxy)-6-methylhept-1-en-4-ol 
• 289472-95-3 4-methyl-2-(tetrahydro-pyran-2-yloxymethyl)-3,6-dihydro-2H-pyran 
• 289472-93-1 (S)-4-Methyl-1-(tetrahydro-pyran-2-yloxy)-pent-4-en-2-ol 
• 104265-24-9 (3R)-4-benzyloxy-3-methyl-butanonitrile 
• 289472-92-0 (2S)-2-(2,2-dibromo-vinyl)-4-methyl-3,6-dihydro-2H-pyran 
• 289472-96-4 (2S)-(4-methyl-3,6-dihydro-2H-pyran-2-yl)-methanol 
• 218898-32-9 (2S)-4-methyl-3,6-dihydro-2H-pyran-2-carbaldehyde 
• 394657-32-0 [(2R,4S)-4-(1-Ethoxy-allyloxy)-2-methyl-hept-6-enyloxymethyl]-benzene 
• 349539-71-5 4-{6-[11-(4-methoxy-benzyloxy)-6-methoxymethoxy-2-methyl-13-(4-methyl-3,6-dihydro-2H-pyran-2-yl)-4-methylene-10-(tetrahydro-pyran-2-yloxy)-trideca-7,12-dienyl]-5,6-dihydro-2H-pyran-2-yl}-but-2-ynoic acid methyl ester 
• 394657-63-7 C₄₄H₆₂Br₂O₈ 
• 349539-69-1 2-{(2R,6R)-6-[(7E,12E)-(2S,6S,10S,11S)-11-(4-Methoxy-benzyloxy)-6-methoxymethoxy-2-methyl-13-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)-4-methylene-10-(tetrahydro-pyran-2-yloxy)-trideca-7,12-dienyl]-5,6-dihydro-2H-pyran-2-yl}-ethanol 
• 312695-83-3 (1E,6E)-(3S,4S,8S,12S)-13-{(2R,6R)-6-[2-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-3,6-dihydro-2H-pyran-2-yl}-3-(4-methoxy-benzyloxy)-8-methoxymethoxy-12-methyl-1-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)-10-methylene-trideca-1,6-dien-4-ol 

Downstream Products

• 312695-87-7 (3Z,9E)-(1R,7S,11S,15S,17R)-7-[(E)-(S)-1-(4-Methoxy-benzyloxy)-3-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)-allyl]-11-methoxymethoxy-15-methyl-13-methylene-6,21-dioxa-bicyclo[15.3.1]henicosa-3,9,19-trien-5-one 
• 115268-43-4 laulimalide 
• 312695-97-9 (Z)-(1R,3S,7S,8S,10S,12S,18R)-7-Hydroxy-12-[(E)-(S)-1-(4-methoxy-benzyloxy)-3-((S)-4-methyl-3,6-dihydro-2H-pyran-2-yl)-allyl]-3-methyl-5-methylene-9,13,22-trioxa-tricyclo[16.3.1.0^8,10]docosa-15,19-dien-14-one 

Relevant academic research and scientific papers

Total synthesis of microtubule-stabilizing agent (-)-laulimalide

An enantioselective first total synthesis of laulimalide (1) is described. Laulimalide, a remarkably potent antitumor macrolide, has been isolated from the Indonesian sponge Hyattella sp. and the Okinawan sponge Fasciospongia rimosa. Laulimalide represents a new class of antitumor agents with significant clinical potential. The synthesis is convergent and involved the assembly of C3-C16 segment 4 and C17-C28 segment 5 by Julia olefination. The sensitive C2-C3 cis-olefin functionality was installed by Yamaguchi macrolactonization of a hydroxy alkynic acid followed by hydrogenation of the resulting alkynoic lactone over Lindlar's catalyst. Initial attempts of intramolecular Still's variant of Horner - Emmons olefination between the C19-phosphonocetate and C3-aldehyde provided a 1:2 mixture of cis- and trans-macrolactones. The trans-isomer was photo-isomerized to a mixture of cis- and trans-isomers. The other key steps involved ring-closing olefin metathesis to construct both dihydropyran units, stereoselective anomeric alkylation to functionalize the dihydropyran ring, stereoselective reduction of the resulting alkynyl ketone to set the C20-hydroxyl stereochemistry, and a novel Julia olefination protocol for the installation of the C13-exomethylene unit. The sensitive epoxide at C16-C17 was introduced in a highly stereoselective manner by Sharpless epoxidation at the final stage of the synthesis.

A macrolactonization-based strategy to obtain microtuble-stabilizing agent (-)-laulimalide

An alternative synthesis of anti-tumor macrolide (-)-laulimalide is described. The synthesis was achieved utilizing Yamaguchi macrolactonization as the key step. The sensitive C2-C3 cis-olefin functionality has been installed by a ma