19822-67-4

Usage

Synthesis Reference(s)

Journal of the American Chemical Society, 99, p. 4192, 1977 DOI: 10.1021/ja00454a066Tetrahedron Letters, 18, p. 2633, 1977

InChI:InChI=1/C10H16O/c1-8-4-5-9(11)10(2,3)7-6-8/h6H,4-5,7H2,1-3H3

Upstream product

• 29414-55-9 6,7-epoxymyrcene 
• 81253-22-7 6-hydroxy-2,6-dimethyl-oct-7-en-3-one 
• 81893-37-0 1-ethenyl-1,5-dimethyl-4-oxohexyl acetate 
• 69875-71-4 1,1-dimethyl-2-(trimethylsiloxy)allyl chloride 
• 115-11-7 isobutene 
• 71328-53-5 5-(1'-bromo-1'-methyl) ethyl-2-methyl-2-vinyltetrahydrofurane 
• 60047-17-8 2-methyl-5-(2'-propyl-2'-hydroxy)-2-vinyltetrahydrofuran 
• 29171-21-9 3,7-dimethyloct-6-en-1-yn-3-yl acetate 
• 63844-95-1 Acetic acid (Z)-7-bromo-3,7-dimethyl-6-oxo-oct-2-enyl ester 
• 63844-94-0 Acetic acid (Z)-7-bromo-6-hydroxy-3,7-dimethyl-oct-2-enyl ester 
• 63707-79-9 (Z)-3,7-dimethyl-6,7-epoxyoct-2-enyl acetate 
• 78-79-5 isoprene 
• 82528-18-5 [2-Methyl-1-((1R,2R)-2-methyl-2-vinyl-cyclopropyl)-propenylsulfanyl]-benzene 
• 82528-18-5 [2-Methyl-1-((1R,2S)-2-methyl-2-vinyl-cyclopropyl)-propenylsulfanyl]-benzene 

Downstream Products

• 163188-34-9 N-p-hydroxyphenyl-3,3,6-trimethyl-5-cyclohepten-2-one-1-carboxamide 

Relevant academic research and scientific papers

Chemoenzymatic synthesis of homochiral (R)- and (S)-karahanaenol from (R)-limonene

Terpinolene oxide, a monoterpene belonging to the p-menthane group, is easily derived from naturally abundant (R)-limonene. It was isomerized with montmorillonite clay catalyst to karahanaenone (2,2,5-trimethylcyclohept-4- en-1-one) by ring enlargement. The enantiomers of the corresponding alcohol, karahanaenol (2,2,5-trimethylcyclohept-4-en-1-ol), known for their individual organoleptic properties, were resolved through Pseudomonas cepacia lipase mediated enantiospecific alcoholysis of its acetate derivative.

Exploiting PdII and TiIII chemistry to obtain γ-dioxygenated terpenoids: Synthesis of rostratone and novel approaches to aphidicolin and pyripyropene A

In nature there are several terpenoids with a characteristic γ-dioxygenated system on the A ring, and many of them show interesting pharmacological properties. We have developed a novel strategy for the synthesis of these terpenoids involving three stages: (a) the selective epoxidation of commercial polyenes, (b) titanium(III)-catalyzed cyclization of the epoxypolyprenes thus obtained, and (c) Pd-mediated remote functionalization of the equatorial methyl group attached at C-4 on ring A of the cyclic terpenoid thus formed. This strategy has proved to be useful for the synthesis of the natural labdane rostratone (1) and related terpenoids, as well as for advanced synthetic approaches toward the pharmacologically active products aphidicolin (2) and pyripyropene A (3).

Carbocyclic Ring Formation by the Intramolecular Reaction between Enol Silyl Ether and Allylic Acetate Moieties

The title reaction of trans-3-acetoxy-4-(4-methyl-3-trimethylsiloxy-3-pentenyl)cyclohexene proceeds in the presence of Et2AlOAr, where Ar=2,6-di-t-butyl-4-methylphenyl, affording stereospecifically the cis isomer of 2,2-dimethylbicyclodec-9-en-3-one.In contrast, the cis-disubstituted cyclohexene compound reacts only sluggishly to produce a mixture of the cis- and trans-fused octalones.Similar stereospecific effect of the allylic double bond configuration on the ease of cyclization has been observed in the synthesis of karahanaenone from 3,7-dimethyl-6-trimethylsiloxy-2,6-octadienyl acetate and related reactions.

Olefin metathesis in supercritical carbon dioxide

Liquid or supercritical carbon dioxide (scCO2) is a versatile reaction medium for ring-opening metathesis polymerization (ROMP) and ring-closing olefin metathesis (RCM) reactions using well-defined metal catalysts. The molybdenum alkylidene complex 1 and ruthenium carbenes 2 and 3 bearing PCy3 or N-heterocyclic carbene ligands, respectively, can be used and are found to exhibit efficiency similar to that in chlorinated organic solvents. While compound 1 is readily soluble in scCO2, complexes 2 and 3 behave like heterogeneous catalysts in this reaction medium. Importantly, however, the unique properties of scCO2 provide significant advantages beyond simple solvent replacement. This pertains to highly convenient workup procedures both for polymeric and low molecular weight products, to catalyst immobilization, to reaction tuning by density control (RCM versus acyclic diene metathesis polymerization), and to applications of scCO2 as a protective medium for basic amine functions. The latter phenomenon is explained by the reversible formation of the corresponding carbamic acid as evidenced by 1H NMR data obtained in compressed CO2. Together with its environmentally and toxicologically benign character, these unique physicochemical features sum up to a very attractive solvent profile of carbon dioxide for sustainable synthesis and production.

Simple synthesis of karahanaenone

Karahanaenone 1 has been prepared from linalool 3. Linalool 3 is cyclized to the corresponding tetrahydrofuran-type cyclic ethers 4a-c on treatment with PhSeCl, N-bromosuccinimide, and 3-chloroperbenzoic acid, respectively. 4a-c on further treatment with various reagents, provide allylic cyclic ether 6 which is converted to 1 via 2.

Synthesis of Karahanaenone

Karahanaenone (1) has been prepared from dehydrolinalyl acetate.Electrochemical epoxidation of dehydrolinalyl acetate provided the corresponding epoxide 6a (75percent) which was converted to keto acetate 7a (82percent) by an electrogenerated acid-catalyzed rearrangement.Hydrogenation followed by alkaline hydrolysis gave 6-hydroxy-2,6-dimethyl-7-octen-3-one (7c) (86percent), which was subjected to thermal dehydration at 200 deg C to give 1 (85percent) via Claisen type rearrangement of the intermediate 2-methyl-2-ethenyl-5-propylidenetetrahydrofuran (2).An alternative route to 1 via thermolysis of the xanthate of 1-(5-ethenyl-5-methyl-2-tetrahydrofuranyl)-1-methylethanol (10b) is also described.

Acid-catalysed Rearrangement of Terpinolene Oxide

The title reaction has been examined in detail and the effects of solvent and the acid catalyst on the nature of the products elucidated.Novel 1,3-dioxolanes, with potential use as aroma chemicals, have been prepared from terpinolene oxide (2) by an efficient method.

ORGANOALUMINIUM ASSISTED REARRANGEMENTS OF FIVE-MEMBERED RING ENOL ETHERS WITH VINYL SUBSTITUENTS

Such organoaluminium reagents as iBu3Al, PhCCAlEt2, and Et2AlSPh mediate the title reactions in three different directions. (1) sigmatropic rearrangement producing 7-membered rings. (2) isomerization to form vinylcyclopropane derivatives and (3) SN2' type reaction with phenylthio anion via oxolane ring opening.

Acid-catalyzed Rearrangements of Linalool Oxide

Reaction of linalool oxide (1) with acids leads to a variety of dehydration products which are shown to be aliphatic dienones and /or monocyclic enones.A mechanism is proposed to account for the generation of all these compounds.

LEWIS ACID CATALYSED PINACOL REARRANGEMENT - A SHORT SYNTHESIS OF KARAHANAENONE

The pinacolic coupling reaction has been effectively used to prepare the unsymmetrical pinacol 2 and this key intermediate underwent a smooth ring enlargement to the monoterpene karahanaenone 3, an odoriferous constituent of Japanese hop and Cypress oil.