328535-13-3

Upstream product

• 243464-39-3 C₅₀H₈₂O₇Si₄ 
• 243464-48-4 C₅₀H₈₂O₇Si₄ 
• 2186-92-7 p-Anisaldehyde dimethyl acetal 
• 243464-42-8 3-(tert-butyl-dimethyl-silanyloxy)-6-(tert-butyl-diphenyl-silanyloxymethyl)-tetrahydro-pyran-2-one 
• 243464-43-9 (3R,6S)-6-(tert-Butyl-diphenyl-silanyloxymethyl)-3-hydroxy-tetrahydro-pyran-2-one 
• 247184-60-7 {3-[(4S,5R)-2-(4-Methoxy-phenyl)-5-methyl-[1,3]dioxan-4-yl]-prop-1-ynyl}-trimethyl-silane 
• 328535-10-0 (2R,4S,5R)-2-(4-Methoxy-phenyl)-5-methyl-4-prop-2-ynyl-[1,3]dioxane 
• 203926-59-4 (2R,3S)-1-(4-Methoxy-benzyloxy)-2-methyl-6-trimethylsilanyl-hex-5-yn-3-ol 
• 203926-60-7 (2R,3S)-1-(4-Methoxy-benzyloxy)-2-methyl-hex-5-yn-3-ol 
• 194038-95-4 {(S)-1-[(R)-2-(4-Methoxy-benzyloxy)-1-methyl-ethyl]-but-3-ynyloxy}-trimethyl-silane 
• 243464-46-2 (2S,5R,10S,11R)-5-(tert-Butyl-dimethyl-silanyloxy)-1-(tert-butyl-diphenyl-silanyloxy)-12-(4-methoxy-benzyloxy)-11-methyl-2,10-bis-trimethylsilanyloxy-dodec-7-yn-6-one 
• 243464-44-0 (2S)-6-benzyloxy-1-(tert-butyldiphenylsilyloxy)-hex-4-yn-2-ol 
• 243464-45-1 (S)-6-(tert-butyl-diphenylsilyloxy)-hexane-1,5-diol 
• 175398-31-9 (S)-6-(tert-butyldiphenylsilyloxy)-5-hydroxyhexanoic acid δ-lactone 

Relevant academic research and scientific papers

Expedient access to the okadaic acid architecture: A novel synthesis of the C1-C27 domain

A newly designed synthetic entry to the C1-C27 domain of okadaic acid has been developed. This incorporates substantial improvements in the preparations of the key okadaic acid building blocks representing the C3-C8, C9-C14, and C16-C27 portions. The synthesis of the C3-C8 lactone used (R)-glycidol as the origin of the C4 stereogenic center and featured a late-stage optional incorporation of the C7 hydroxyl group. The complementary C9-C14 fragment was synthesized in a concise route from (R)-3-tert-butyldimethylsilyloxy-2-methylpropanal and propargyl bromide. Assembly of the C3-C14 spiroketal-containing intermediate from the constituent fragments revealed a dramatic effect of C7 functionalization upon spiroketalization efficiency. In contrast, both (9E)- and (9Z)-enones converged readily to the C8 spiroketal upon treatment with acid. Modifications to the central C16-C27 fragment of okadaic acid included the early replacement of benzylic protecting groups by more suitable functionalities to facilitate both the generation of the C15-C27 intermediate and the deprotection of the final products. These modular building blocks were deployed for the synthesis of the C1-C27 scaffold of 7-deoxyokadaic acid. This work demonstrates improvements in the formation of versatile okadaic acid intermediates, as well as a reordering of fragment couplings. This alternative order of coupling was designed to promote the late stage incorporation of nonnatural lipophilic extensions from the C27 terminus.

Abbreviated synthesis of the C3-C14 (substituted 1,7-dioxaspiro[5.5]undec-3-ene) system of okadaic acid.

[formula: see text] Described is a novel, concise, and flexible synthesis of the C3-C14 portion of okadaic acid. A substituted valerolactone (C3-C8) was prepared in three steps and alpha-hydroxylated using Davis' oxaziridine. Conjugate addition of dimethy