93215-97-5

Upstream product

• 851520-66-6 (3R)-3-isopropyl-6-methyl-7-oxabicyclo[4.1.0]heptane 
• 1195-31-9 (+)-p-menth-1-ene 

Downstream Products

• 339157-71-0 (1R,5R)-5-isopropyl-2-methylidene-1-(pent-4-enyl)cyclohexanol 
• 339157-72-1 (R)-1-Chloromethyl-4-isopropyl-2-pent-4-enyl-cyclohexene 
• 339157-70-9 Acetic acid (R)-4-isopropyl-2-pent-4-enyl-cyclohex-1-enylmethyl ester 
• 339157-69-6 (1R,5R)-5-isopropyl-2-methylidene-1-(pent-4-enyl)cyclohexyl acetate 

Relevant academic research and scientific papers

Synthesis of the Alleged Natural Monoterpenoid α-Santolinenone

Authentic α-santolinenone ( = (+)-(4R)-1(7)-p-menthen-2-one; (+)-1) is made available for the first time in 30 percent overall yield from (+)-(4R)-p-menthene ((+)-2) via the diastereomeric allylic alcohols (+)-4a/(+)-4b, which are oxidized to (+)-1 with Ag2CO3/Celite.Yields are good, except for the last stage; indeed, only alcohol (+)-4a, with equatorial OH-group, undergoes oxidation, and (+)-1 is partly substracted via a hetero Diels-Alder dimerization giving a mixture of the diastereomeric dihydropyrans (+)-5a/(+)-5b.When Cr(VI) reagents are used, (+)-4a/(+)-4b mainly give phelandral (6) and carvotanacetone (7).MnO2 reacts too sluggishly with (+)-4a/(+)-4b.A camphor pyrolyzate, previously thought to be 1 must be a different compound, probably 7.

Synthesis of (-)-erythrodiene and (+)-7-epispirojatamol via intramolecular Pd-catalyzed allylzincation

Two spirobicyclic sesquiterpenoids, (-)-erythrodiene (1) and (+)-7-epispirojatamol (30), were synthesized in enantiomericaliy pure form via an intramolecular allylzincation process. The allylzinc species were formed in the presence of Et2Zn via transmetallation of a catalytically generated allylpalladium intermediate. Several Pd catalysts were tested for this transformation, and [Pd(OAc)2]/Bu3P (1 equiv.) was found to be, by far, the most effective. Whereas the preparation of 1 involved allylzincation of a tethered terminal olefin, 30 was formed via a novel intramolecular allyl zincation of a methyl ketone. Both reactions showed the same stereochemical preference, yielding the spirobicyclic products in 95:5 and 4:1 diastereoisomer ratios, respectively.