26934-83-8

Upstream product

• 75-16-1 methylmagnesium bromide 
• 599164-90-6 (2R,5S,10S)-6,10-Dimethyl-spiro[4.5]dec-6-ene-2-carboxylic acid methyl ester 
• 124482-30-0 (S)-3-methyl-2-methylenecyclohexanone 
• 599164-89-3 methyl (2R,5S,10S)-10-methyl-6-oxo-spiro[4.5]decane-2-carboxylate 
• 596094-27-8 methyl (2R,5S,10S)-10-methyl-6-methylene-spiro[4.5]decane-2-carboxylate 
• 596094-23-4 tert-butyl (5S,10S)-10-methyl-6-oxo-spiro[4.5]dec-2-ene-2-carboxylate 
• 596094-26-7 tert-butyl (2R,5S,10S)-10-methyl-6-oxo-spiro[4.5]decane-2-carboxylate 
• 917-54-4 methyllithium 
• 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 
• 30320-55-9 Acetic acid (3R,5S,8R,10S)-3-(1-hydroxy-1-methyl-ethyl)-6,10-dimethyl-spiro[4.5]deca-1,6-dien-8-yl ester 
• 52528-49-1 methyl (2RS,5R^*,10R^*)-6,10-dimethylspiro<4.5>dec-6-ene-2-carboxylate 
• 40790-56-5 2,6-dimethyl-2-cyclohexen-1-one 
• 169898-78-6 1,5-dimethyl-6-methylenecyclohexene 

Relevant academic research and scientific papers

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.

Claisen rearrangement strategy in alkenyl dihydropyran leading to total synthesis of (+)-α-vetispirene and (-)-agarospirol

Total synthesis of (+)-α-vetispirene and (-)-agarospirol based on a Claisen rearrangement has been achieved. This is the first example of a Claisen rearrangement in an enantio-enriched alkenyl bicyclic dihydropyran system with perfect asymmetric transmission. Copyright

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.

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.

A New Synthesis of (+/-)-Agarospirol and (+/-)-Hinesol

(+/-)-Agarospirol (8) and (+/-)-hinesol (9) were simultaneously synthesized via a useful synthon in the synthesis of spirovetivane-type sesquiterpenes, i.e., (2S*,5S*,10R*)-2-hydroxy-6,10-dimethylspirodec-6-en-8-one (1), which had previously been prepared from the corresponding phenolic α-diazoketone via the spiro-annelation reaction and subsequent stereo-controlled Birch reduction, both reported in our previous communications.Keywords-(+/-)-agarospirol; (+/-)-hinesol; spirovetivane-type sesquiterpenes; useful synthon; (2S*,5S*,10R*)-2-hydroxy-6,10-dimethylspirodec-6-en-8-one

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.