118333-87-2

Upstream product

• 50727-94-1 (2R,3R)-3-methyl-3-(4-methyl-3-pentenyl)oxiranemethanol 
• 106-24-1 Geraniol 
• 870-63-3 prenyl bromide 
• 122616-28-8 (1S,4R,6R,8R)-4-((R)-2-Benzenesulfonyl-1,5-dimethyl-hex-4-enyl)-11,11-dimethyl-5-oxa-3-thia-tricyclo[6.2.1.0^1,6]undecane 
• 10281-56-8 (R)-3,7-dimethyl-1,6-octadiene 
• 7270-50-0 6-methyl-1,5-heptadiene 
• 203315-97-3 (R)-2,2-dimethyl-3-(3-methylpent-4-en-1-yl)oxirane 
• 160488-95-9 (2S,3R)-3,7-dimethyl-6-octene-1,2-diol 
• 122616-29-9 (1S,4R,6R,8R)-4-((R)-1,5-Dimethyl-hex-4-enyl)-11,11-dimethyl-5-oxa-3-thia-tricyclo[6.2.1.0^1,6]undecane 

Downstream Products

• 2385-77-5 (R)-Citronellal 

Relevant academic research and scientific papers

Enantioselective total synthesis of (-)-curcuquinone via regioselective chromium-mediated benzannulation

(Chemical Equation Presented) A short and efficient, high-yielding enantioselective total synthesis of the marine natural product (-)-curcuquinone 1 is reported involving a regioselective [3 + 2 + 1]-benzannulation reaction as the key step. Additionally, this strategy allows the isolation of curcuhydroquinone monomethyl ether 9 as an intermediate of the benzannulation reaction and its subsequent further protection toward diversified hydroquinones.

A study towards the synthesis of (-)-atrop-abyssomicin C core

An attempt to synthesize the cyclohexane core of antibiotic abyssomicin C is described. The initial, protecting group-free approach (relying on internal protection) failed and had to be modified, in order to allow for efficient deprotection of the acid-sensitive cyclization precursor in the penultimate synthetic step. Thus, a pyranoside structural unit was used as a latent lactone/ester functionality, which was deprotected via thioacetalization/hydrolysis/oxidation sequence, to give the δ-valerolactone-type cyclization precursor. Unfortunately, the key cyclization reaction was not feasible, even after structural modification of the cyclization precursor. Reluctance towards cyclization turned out to be a general property of (at least some) Δ7-unsaturated esters, which required the development of a new strategy for this type of transformation.

Total synthesis and biological evaluation of (-)-atrop-abyssomicin C

Enantioselective synthesis of a marine antibiotic (-)-atrop-abyssomicin C was accomplished in 21 steps, in 1.8% overall yield (4%, based on the recovered starting material). The key steps of the synthesis are the formation of the functionalized cyclohexane core by an organocatalyzed Tsuji-Trost reaction, the formation of a tricyclic spirotetronate unit by a gold-catalyzed reaction sequence and the highly efficient eleven-membered ring closure by a Nozaki-Hiyama-Kishi reaction. Biological tests showed all abyssomicin derivatives to possess strong antibacterial activity against methicillin resistant S. aureus strains; however, they also proved to be cytotoxic, both to malignant and to normal somatic cells. The Royal Society of Chemistry.

Total synthesis of (-)-atrop-abyssomicin C

Rolling in the deep: An enantioselective synthesis of a marine antibiotic (-)-atrop-abyssomicin C (see scheme) is described. The key steps of the synthetic sequence are the application of dual catalysis in the formation of the cyclohexane core, the gold-catalyzed formation of a tricyclic spirotetronate unit, and a highly efficient eleven-membered ring closure by a Nozaki-Hiyama-Kishi reaction. Copyright

Composition of the cloacal gland secretion of tuatara, Sphenodon punctatus

The lipophilic content of the cloacal gland secretion of the tuatara (Sphenodon punctatus) was investigated. GC/EI-MS Analysis of CH2Cl2 extracts of the secretions revealed triacylglycerols as major glandular constituents. Twelve major medium-chain fatty acids were found to be conjugated to glycerol in different combinations, resulting in complex mixtures. These acids were identified by transesterification and subsequent derivatization of natural samples, and their structures were verified by synthesis. The natural glycerides contain predominantly three of the following acids: octanoic (A), (E)- and (Z)-oct-4-enoic (B and C, resp.), (4E,6Z)-octa-4,6-dienoic (tuataric acid;D), (R)-2,6-dimethylheptanoic (E), (R)-2,6-dimethylhept-5-enoic (F), (Z)-dec-4-enoic (G), (4Z,7Z)-deca-4,7-dienoic (H), (R)-3,7-dimethyloct-6-enoic (I), (R)-4,8-dimethylnon-7-enoic (J), (2R,6S)-2,6,10-trimethylundec-9-enoic (K), and (2R,5E)-2,6,10-trimethylundeca-5,9-dienoic acids (L). Several additional acids, occurring in trace amounts only, were tentatively identified by MS. The elucidation of the absolute configuration of the acids was performed by GC on chiral phases. Individual tuatara show specific mixtures of glycerides with up to 100 components. The individual mixtures may permit individual recognition because the bouquets seem to be stable over years.

Stereochemistry of female-specific normonoterpenes, sex pheromone candidates from the acarid mite, Tyreophagus sp. (Astigmata: Acaridae)

Two normonoterpenes were detected from an unidentified Tyreophagus sp. as new female-specific components. Both planar structures were identified to be 2,6-dimethyl-5-heptenal (1) and 2,6-dimethyl-5-hepten- 1-ol (2) by GC/MS co-chromatography with synthetic 1 and 2. The stereochemistry of 2 was determined to be R by a GC analysis with a chiral column, while that of 1 was presumed to be similar to 2 based on the biosynthetic aspects.

Zirconium-catalyzed asymmetric carboalumination of alkenes: ZACA-lipase-catalyzed acetylation synergy

ZACA-lipase-catalyzed acetylation tandem reactions provide highly efficient and selective routes to either (R)- or (S)-2-methyl-1-alkanols, making, for the first time, the ZACA-based asymmetric synthesis of 2-methyl-1-alkanols widely applicable and satisfactory.

Semiochemicals of the scarabaeinae. VII: Identification and synthesis of ead-active constituents of abdominal sex attracting secretion of the male dung beetle, Kheper subaeneus

Using gas chromatography with flame ionization detection (FID) and electroantennographic detection (EAD) in parallel, butanoic acid, skatole, and (E)-2,6-dimethyl-6-octen-2-ol were identified as constituents of the abdominal sex-attracting secretion of the male dung beetle, Kheper subaeneus, which reproducibly elicited EAD responses in male and female antennae. This is the first report of the occurrence of (E)-2,6-dimethyl-6-octen-2-ol as a natural product, for which the name (E)-subaeneol is proposed. In some experiments, a few other constituents of the secretion also gave reproducible responses in specific male and female antennae but did not elicit responses when the analyses were repeated with other antennae. The major volatile constituent of the secretion, identified as (S)-(+)-2,6-dimethyl-5-heptenoic acid, is one of these EAD-active compounds. Both this compound and (E)-2,6-dimethyl-6-octen-2-ol were synthesized from authentic starting materials for comparison with the natural products.

Total synthesis of the serine/threonine-specific protein phosphatase inhibitor tautomycin

A convergent, asymmetric synthesis of the protein phosphatase inhibitor, tautomycin, is described. The natural product was constructed by joining two major fragments of comparable complexity at the C21-C22 bond. Absolute stereochemistry of the C1-C21 ketone originates from (S)-citronellene and (2R,3S)-geraniol epoxide. The anti stereochemical relationships at C6-C7 and C18-C19 were introduced with Duthaler's chiral titanium propionic enolate. Syn stereochemical relationships at C13-C14 and C23-C24 were established using an Evan's oxazolidinone chiral auxiliary. The spiroketal was efficiently constructed via a one-pot double-alkylation-spirocyclization sequence with acetone N,N-dimethylhydrazone serving as the central linchpin. Final coupling of the two halves using a chelation-controlled Mukaiyama aldol addition followed by deprotection yielded synthetic tautomycin that is identical to the natural product.

ASYMMETRIC SYNTHESIS VIA HETEROCONJUGATE ADDITION USING ELIEL'S CAMPHOR TEMPLATE

A new asymmetric synthesis is reported that includes carbon-carbon bond formation based upon heteroconjugate addition with Eliel's 1R-(+)-camphor derivative as a template.This method showed high enantiomeric excess under chelation control affected by the solvent polarity and by the salt present in the reaction media. (+)-citronellal was synthesized as a proof of this method.