59331-08-7

Upstream product

• 75-16-1 methylmagnesium bromide 
• 52528-49-1 methyl (2RS,5R^*,10R^*)-6,10-dimethylspiro<4.5>dec-6-ene-2-carboxylate 
• 917-64-6 methyl magnesium iodide 
• 121840-74-2 6,10-Dimethyl-spiro[4.5]dec-6-ene-2-carboxylic acid methyl ester 
• 917-54-4 methyllithium 
• 166373-58-6 (4E)-3-(tert-butyldimethylsiloxy)hex-4-enal 
• 78074-13-2 2-hydroxymethyl-3-methylcyclohexanone 
• 30310-78-2 (3R,5S,8R,10S)-3-(1-Hydroxy-1-methyl-ethyl)-6,10-dimethyl-spiro[4.5]deca-1,6-dien-8-ol 
• 121741-13-7 6-Hydroxy-6,10-dimethyl-spiro[4.5]decane-2-carboxylic acid methyl ester 
• 121840-75-3 6-Methyl-10-methylene-spiro[4.5]decane-2-carboxylic acid methyl ester 
• 121741-12-6 6-Methyl-10-oxo-spiro[4.5]decane-2-carboxylic acid 
• 121741-18-2 6-Hydroxy-6,10-dimethyl-spiro[4.5]decane-2-carboxylic acid 

Relevant academic research and scientific papers

Stereoselective total synthesis of (±)-α-vetispirene, (±)-hinesol, and (±)-β-vetivone based on a Claisen rearrangement

The stereoselective total syntheses of (±)-α-vetispirene, (±)-hinesol, and (±)-β-vetivone were accomplished based on a Claisen rearrangement in an alkenyl bicyclic dihydropyran system. The most striking feature of this approach is that the Claisen rearrangement of bicyclic dihydropyran proceeds stereoselectively to provide a multi-functionalized spiro[4.5]decane, which is an efficient precursor for the synthesis of the vetivane sesquiterpenes.

A unified, RCM anchored approach to spiro[4.5]decane-based sesquiterpenoids: Collective synthesis of (±)-α & β-vetispirenes, (±)-β-vetivone, (±)-agarospirol and (±)-hinesol

Collective syntheses of five spiro[4.5]decane framework bearing sesquiterpenoids, namely, α & β-vetispirenes, β-vetivone, agarospirol and hinesol as well as formal synthesis of axenol and gleenol from a readily available precursor cyclohexanone-β-ketoester via the intermediacy of a versatile intermediate (2,10-dimethylspiro[4.5]dec-1-en-6-one) have been accomplished in a concise manner.

Connective synthesis of spirovetivanes: Total synthesis of (±)-agarospirol, (±)-hinesol and (±)-α-vetispirene

A concise, connective synthesis of naturally occurring spirovetivanes 1 and 3, in racemic form, is presented. This novel approach involves the efficient assembly of the advanced intermediate 12 through a unique spiroannulation protocol. Wiley-VCH Verlag GmbH & Co. KGaA1 69451 Weinheim, Germany, 2004.

A phosphine-catalyzed [3+2] cycloaddition strategy leading to the first total synthesis of (-)-hinesol

In one step, the skeleton of cis-spirovetivanes was constructed with high stereoselectivity by the phosphine-catalyzed [3+2] cycloaddition reaction of tert-butyl 2,3-butadienoate or 2-butynoate with 3-methyl-2-methylenecyclohexanone (5). This method was exemplified by the first highly efficient total synthesis of natural product (-)-hinesol, which is an active ingredient of cerebral circulation and metabolism improvers.

Synthetic photochemistry. LXVII. A total synthesis of (±)-hinesol and (±)-agarospirol via retro-benzilic acid rearrangement

A mild base-catalyzed retro-benzilic acid rearrangement of a proto-photocycloadduct, formed in highly stereoselective photoaddition of methyl 2,4-dioxopentanoate to 1,5-dimethyl-6-methylene-1-cyclohexene, afforded a spiro[4.5]decenedione derivative. Reductive elimination of the α-dicarbonyl function and C1-homologation furnished (±)-hinesol and (±)-agarospirol.

A NOVEL SKELETAL REARRANGEMENT OF BICYCLO(2.2.2)OCTENES THROUGH BICYCLO(3.2.1)OCTENE SYSTEM: SYNTHESIS OF (+/-)-HINESOL AND (+/-)-10-epi-HINESOL

Acid catalysed rearrangement of the endo-alcohol (9) leads to the ketones (11) and (12) having the bicyclo(3.2.1) and bicyclo(2.2.2) moieties.An efficient entry into spiro(4,5)decane and eremane system, as exemplified by the total synthesis of (+/-)-hinesol (2) and its 10-epimer (3) is reported.

The total synthesis of (+/-)hinesol and (+/-)epihinesol

The tricyclic ketal ketones 15a and 15b have been obtained in an isomeric ratio of 9:1 (4 5 6 7 8 9 10 11 12 13 14 15a + 15b).Compound 15a was converted in seven (or eight) steps to (+/-)epihinesol (3) 29 32 48 49 47 (or 32 39 38 44 47) 50 3> and compound 38 was transformed into (+/-)hinesol (2) in five steps (38 76 77 62 63 2).The identity of epihinesol and agarospirol was confirmed by formation of a common epoxide.