539802-71-6

Upstream product

• 110202-07-8 (E)-4-Methyl-6-(2',6',6'-trimethyl-1'-cyclohexenyl)hex-3-en-1-ol 
• 171291-29-5 2-[(E)-6-iodo-3-methylhex-3-enyl]-1,3,3-trimethylcyclohexene 

Downstream Products

• 540482-87-9 (+)-(R)-manoalide 
• 539802-73-8 (+)-(6R)-3-[(E)-4'-methyl-6'-(2'',6'',6''-trimethylcyclohex-1''-enyl)hex-3'-enyl]-6-(5'''-triethylsilylfuran-3'''-yl)-5,6-dihydropyran-2-one 

Relevant academic research and scientific papers

Synthesis of (+)-manoalide via a copper(I)-mediated 1,2-metalate rearrangement

An enantiospecific synthesis of the phospholipase A2 inhibitor (+)-(4R)-manoalide is reported in which all 25 carbons of the sesterterpenoid skeleton are constructed from 3-furaldehyde, trimethylalane, oxirane, CO, β-ionone, and propargyl bromide. The overall yield for the longest linear sequence (12 steps) is 12%. Key steps include (a) a zirconium-catalyzed carboalumination reaction to construct the C10-C11 trisubstituted alkene, (b) a Cu(I)-mediated 1,2-metalate rearrangement to construct the C6-C7 trisubstituted alkene, (c) a Sharpless kinetic resolution to secure the (4R)-stereochemistry, (d) generation of a 5-stannyl-2,3-dihydrofuran by Mo-catalyzed cycloisomerization of a homopropargylic alcohol, and (e) construction of the hydroxyfuranone ring by photooxidation of a silylfuran.