470467-03-9

Upstream product

• 994-30-9 triethylsilyl chloride 
• 60410-16-4 (1R,4S)-4-hydroxy-2-cyclopentene-1-yl acetate 
• 1259030-61-9 (3R,4S,5S)-5-(8-tert-butyldiphenylsilyloxyoctyl)-3-triethylsilyloxy-4-(2-triethylsilyloxyethyl)cyclopent-1-ene 
• 620114-82-1 (3aS,4S,6S,6aS)-4-[8-(tert-Butyl-diphenyl-silanyloxy)-octyl]-6-iodo-hexahydro-cyclopenta[b]furan-2-one 
• 1026808-56-9 {(1S,2S,5R)-2-[8-(tert-Butyl-diphenyl-silanyloxy)-octyl]-5-hydroxy-cyclopent-3-enyl}-acetic acid methyl ester 
• 620114-81-0 (1S,2S)-2-([8-{(tert-butyldiphenylsilyl)oxy}octyl]-4-cyclopentenyl)acetic acid 
• 470467-01-7 (3aS,4S,6aR)-4-(8-tert-butyldiphenylsilyloxyoctyl)-3,3a,4,6a-tetrahydro-2H-cyclopenta[b]furan-2-one 
• 470466-98-9 (4S,1R)-4-[8-{(tert-butyldiphenylsilyl)oxy}octyl]-2-cyclopentenyl acetate 
• 470467-00-6 (1S,2S)-2-([8-{(tert-butyldiphenylsilyl)oxy}octyl]-4-cyclopentenyl)ethanal 
• 470466-99-0 (4S,1R)-4-[8-{(tert-butyldiphenylsilyl)oxy}octyl]-2-cyclopenten-1-ol 
• 470466-96-7 (4S,1S)-4-[8-{(tert-butyldiphenylsilyl)oxy}octyl]-2-cyclopenten-1-ol 
• 470467-02-8 {(1S,2S,5R)-2-[8-(tert-Butyl-diphenyl-silanyloxy)-octyl]-5-triethylsilanyloxy-cyclopent-3-enyl}-acetic acid methyl ester 

Downstream Products

• 470467-04-0 C₄₀H₆₄O₂Si₂ 
• 85551-10-6 4-oxo-5α-(2Z)-pentenyl-2-cyclopentene-1α-octanoic acid 
• 71606-07-0 13-epi-12-oxo-phytodienoic acid 

Relevant academic research and scientific papers

Stereoselective synthesis of epi-jasmonic acid, tuberonic acid, and 12-oxo-PDA

epi-Jasmonic acid (epi-JA) and tuberonic acid (TA) were synthesized from the key aldehyde, all cis-2-(2-hydroxy-5-vinylcyclopentyl)acetaldehyde (14), which was in turn prepared stereoselectively from the (1R)-acetate of 4-cyclopentene-1,3-diol (10) through SN2-type allylic substitution with CH2CHMgBr followed by Mitsunobu inversion, Eschenmoser-Claisen rearrangement, and regioselective Swern oxidation of the corresponding bis-TES ether (13). Wittig reaction of the aldehyde 14 with [Ph3P(CH 2)Me]+Br- followed by oxidation afforded epi-JA (3) stereoselectivity over the trans isomer. Similarly, TA (5) was synthesized. Furthermore, the above findings were applied successfully to improve the total efficiency of the previous synthesis of 12-oxo-PDA (1).

Efficient total synthesis of 12-oxo-PDA and OPC-8:0

Although the supply of 12-oxo-PDA (1) and OPC-8:0 (2), the metabolites in the linolenic acid cascade leading to epi-jasmonic acid, is in demand for biological investigations, the previous syntheses of these metabolites suffer from low efficiency. Recently, we established a reaction to install an alkyl group onto the ring of cyclopentene monoacetate 4 by using a reagent system consisting of RMgCl (3 equiv) and CuCN (cat). The reaction was applied to ClMg(CH2)8OTBDPS (11) with modification by which the quantity of 11 could be reduced to 2 equiv without decreasing efficiency. The product 12 obtained in 88% yield with 92% regioselectivity was successfully transformed into the key iodolactone 17 in good yield, from which 12-oxo-PDA (1) and OPC-8:0 (2) were synthesized as described in Schemes 3 and 5 through construction of the cis side chain by Wittig reaction. Note that the Wittig reaction proceeded with high cis selectivity of > 95%, which is higher than in similar cases reported previously. Synthesis of the 13-isomers of 1 and 2 was also accomplished. With these compounds in hand, the epimerization speed of 1 and 2 was investigated to rule out overestimation of the finding in the literature that 1 and 2 change to the 13-epimers easily. Instead, we observed that the compounds are quite stable at room temperature for an extended period of days under slightly acidic and neutral conditions.

Controlled syntheses of 12-oxo-PDA and its 13-epimer

Stereoselective synthesis of 12-oxo-PDA starting with (1R,3S)-cyclopenten-1,3-diol monoacetate is accomplished. Key transformations are copper-catalyzed installation of the C(1)-C(8) chain onto the cyclopentene ring and construction of the C(14)-C(18) cha