A Facile One-step Synthesis of<i>cis</i>-2-Cyclopentene- and<i>cis</i>-2-Cyclohexene-1,4-diols from the Corresponding Cyclodienes

Kaneko, Chikara; Sugimoto, Akihiro; Tanaka, Seiji

doi:10.1055/s-1974-23462

Cited by 95 publications

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“…cyclopentadiene by singlet oxygen has been chosen as a model reaction. The explosive endoperoxide, which is formed as an intermediate, was reduced to give 2-cyclopenten-1,4-diol (see Scheme 1), which is of pharmaceutical importance [8] and is produced as batch product where the explosive intermediate is formed in greater amounts [9,10].…”

Section: Introductionmentioning

confidence: 99%

Photochemical Generation and [4+2]‐Cycloaddition of Singlet Oxygen in a Falling‐Film Micro Reactor

Jähnisch¹,

Dingerdissen

2005

Chem Eng & Technol

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The presented falling‐film microreactor is suited for the generation and reaction of singlet oxygen for the photo‐oxygenation of olefins and allows for the first time conversions on a preparative scale. Due to the short holdup the concentration of the explosive endoperoxide is low in the whole reactor system and the endoperoxide is reduced to the final product immediately after leaving the reactor. The results show the feasibility of this reaction although the process is not yet optimized.

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Section: Introductionmentioning

confidence: 99%

Photochemical Generation and [4+2]‐Cycloaddition of Singlet Oxygen in a Falling‐Film Micro Reactor

Jähnisch¹,

Dingerdissen

2005

Chem Eng & Technol

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“…The mixture was diluted with water and extracted with ether. 4a,lO@-Dimet/z~~l-5-I1ydr.oxydecal-3-ot1e, 18 Liquid ammonia (70 ml) was distilled through a tube containing sodium hydroxide into a dry flask containing epoxy ketones 1 7 (1.14 g). Lithium (0.2 g) was added in small pieces to the stirred solution.…”

Section: Methodsmentioning

confidence: 99%

“…Treatment of 2 with the triplienplphosphite-ozone complex (17) gave enclo-peroxide 3 in only 155i yield. Attempted conversion of the initially formed cyclic peroxide i~z sitic to the more stable allylic diol 13 by photooxygenation in the presence of thiourea (18) was unsuccessful. The crude photolysis product contained the same mixture of compounds (tlc) as the product obtained in the absence of thiourea.…”

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confidence: 99%

“…The ketol so obtained was assigned the relative stereochemistry shown in 18 on the basis of pyridine induced shifts of the C-10 methyl (A6 +0.04) in the pmr spectrum (2,10,27). Removal of the carbonyl in 18 was effected in over 95% yield by thio ketal formation followed by desulfurization with Raney nickel. The crystalline product obtained was identical in ir, pmr, mass spectrum, and tlc behavior with (-)-geosmin (2,281.…”

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confidence: 99%

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Metabolites of bird's nest fungi. Part 6. The synthesis of (±)-cybullol and a new synthesis of (±)-geosmin

Ayer¹,

Browne²,

Fung³

1976

Can. J. Chem.

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. Can. J. Chem. 54,3276 (1976).The stereoselective transformation of 6,10-dimethyl-4-octal-3-one (8) to racemic cybullol (I), a mztsbolite of C y u r l 7~~~ hlr1ler.i Brodie. is reported. The transformation 4.1O-dimethyl-4-octal-3-one to (i-)-geosmin (15) is described. The results of the photosensitized [4 + 21 cycloaddition of oxygen to a number of IO-metl1yl-2,4-hexalins are discussed. WILLIAM A. AYER, LOIS M. BROWNE et STEVEN FUNG. Can. J. Chem. 54, 3276 (1976).On rapporte la transformation stCrCosClective de la dimethyl-6,10 octal-4 one-3 (8) en cybullol racemique (I), un mitabolite du Cj.utl~us bzrlleri Brodie. On dCcrit la transformation de la dimethyl-4,10 octal-4 one-3 en (i-)-geosn~ine (15). On discute des resultats obtenus lors de la cycloaddition photosensibilisCe [4 + 21 de I'oxygene B un certain nombre de methyl-I0 hexalines-2,4.[Traduit par le journal]Examination of the metabolites of some of the small gastromycetous fungi known as Bird's Nest fungi (Nidulariaceae) in these laboratories has led to the isolation of a variety of terpenoid (e.g., Cyathut helenae Brodie (I), Cyathus bulleri Brodie (2)) and non-terpenoid (e.g., Cyathu~ intermedius (3)) constituents. We now wish to report the stereoselective synthesis of racemic cybullol (I), a degraded eudesmane-type sesquiterpene produced by C. hulleri (2). At the same time we report a new, high yield, synthesis of the related fungal metabolite, geosmin (4).Cybullol, 1, is a dimethyldecalindiol in which the two hydroxyl groups bear a cis-1,4-relationship in a trans-fused system. A facile synthetic approach to a cis-l,4-cyclohexanediol system involves the [4 + 21 cjlcloaddition of a 1,3-cyclohexadiene with molecular oxygen to give a cyclic peroxide, followed by reduction, as outlined in Scheme 1.It is well documented that the photooxygenation of steroidal conjugated dienes is sensitive to steric effects (oxygen as a dienophile, ref. 5a; sensitized photooxygenation of olefins, ref. 56) and that the endo-peroxide produced is usuall) on the side opposite to nearby angular methyl groups. However, relatively few examples of photooxygenation of hexalin dienes have been reported (6). In order to further investigate the stereochemistry of photooxygenation of hexalin systems as well as to provide a model compound for a 13C nuclear magnetic resonance (cmr) study reported elsewhere (7), we examined initially the photooxygenation of 10-methyl-2,4-hexalin, 4 (Scheme 2). The diene 4 was prepared from lO-methyl-4-octal-3-one (8) by the method of Dauben et al. (9). Photosensitized oxygenation (5, 6) in the presence of eosin Y yielded the endo-peroxide 5 and the y-hydroxyenone 6. Catalytic hydrogenation of the etzdo-peroxide gave a crystalline diol, which was assigned the relative stereo- For personal use only.

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“…Metabolic carotanoids derivable from 2 were therefore surveyed in the extracts of mature leaves that had hardened to a deep green color and of senescent leaves dried and partly yellowed, using as a guide some carotane acids chemically 3 ) The methyl ester and three rearranged peroxide derivatives of 2 were therefore isolated and their structures elucidated. These compounds (3)(4)(5)(6) are considered to be the first derivatives of 2 in the carotane peroxide metabolic pathway. In this paper, the authors describe the isolation and identification of these highly modified carotane sesquiterpenes, together with their chemical conversion from 2.…”

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Isolation of Four Novel Carotanoids as Possible Metabolites of Rugosic Acid A inRosa rugosaLeaves

Hashidoko

Tahara

Mizutani

1991

Agricultural and Biological Chemistry

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A Facile One-step Synthesis ofcis-2-Cyclopentene- andcis-2-Cyclohexene-1,4-diols from the Corresponding Cyclodienes

Cited by 95 publications

References 0 publications

Photochemical Generation and [4+2]‐Cycloaddition of Singlet Oxygen in a Falling‐Film Micro Reactor

Photochemical Generation and [4+2]‐Cycloaddition of Singlet Oxygen in a Falling‐Film Micro Reactor

Metabolites of bird's nest fungi. Part 6. The synthesis of (±)-cybullol and a new synthesis of (±)-geosmin

Isolation of Four Novel Carotanoids as Possible Metabolites of Rugosic Acid A inRosa rugosaLeaves

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