Stereoselective total synthesis of (±)-3-oxosilphinene through intramolecular Diels–Alder reaction

Ihara, Masataka; Kawaguchi, Akihiro; Ueda, Hiroyuki; Chihiro, Masatoshi; Fukumoto, Keiichiro; Kametani, Tetsuji

doi:10.1039/p19870001331

Cited by 15 publications

(18 citation statements)

References 3 publications

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“…Syntheses of monocyclic and bicyclic terpenes as 655, 658, and 660. [470] Wolff rearrangement was involved at a late, tricyclic stage in syntheses of isocomene, 656 Ǟ 657 Ǟ 658, [471] 3-oxosilphinene, [472] and pentalenene, 659 Ǟ 660. [473a] The linear triquinane capnellene (662), isolated from the soft coral Capnella imbricata, was synthesized by ring contraction of 661.…”

Section: Natural Products and Related Targetsmentioning

confidence: 99%

100 Years of the Wolff Rearrangement

2002

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The conversion of α‐diazo ketones into ketenes, and products derived therefrom, was discovered by Wolff in 1902. Major applications of the Wolff rearrangement, such as the Arndt−Eistert reaction (homologation of carboxylic acids) and the ring contraction of cyclic ketones, have been with us for some while. Nevertheless, substantial progress has been made recently. The reaction mechanism has been explored by means of matrix isolation, time‐resolved spectroscopy, and computation. Full retention of configuration of the migrating group has been established by using enantioselective chromatography. The Arndt−Eistert reaction has witnessed a renaissance in the field of natural products, in particular β‐amino acids and β‐peptides. Ring‐contracting Wolff rearrangements and ketene cycloadditions have been applied in syntheses of increasingly complex, biologically active target molecules. These accomplishments, as well as unsolved problems, are addressed in the present review. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Section: Natural Products and Related Targetsmentioning

confidence: 99%

100 Years of the Wolff Rearrangement

2002

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“…According to the literature, 41 the ylide of allyltriphenylphosphonium bromide (36) is usually generated and reacted at room temperature. In our case, following these conditions, we obtained very low amounts of (18E)-nor-29-MOS (37).…”

Section: Chemistrymentioning

confidence: 99%

29-Methylidene-2,3-oxidosqualene Derivatives as Stereospecific Mechanism-Based Inhibitors of Liver and Yeast Oxidosqualene Cyclase

Ceruti¹,

Rocco²,

Viola³

et al. 1998

J. Med. Chem.

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Two pairs of isomers (18Z)- (8), (18E)-29-methylidene-2,3-oxidohexanorsqualene (21), and (18Z)- (31), (18E)-29-methylidene-2,3-oxidosqualene (34), have been obtained in a fully stereospecific manner, as inhibitors of rat and yeast oxidosqualene cyclase. A new method for the synthesis of C22 squalene aldehyde 2,3-epoxide is reported, as well as that of other 19-modified 2,3-oxidosqualene analogues. We found that the activity is the opposite in the two series: the (E)-hexanormethylidene 21 and the (Z)-methylidene 31 are potent and irreversible inhibitors of oxidosqualene cyclase, while (Z)-hexanormethylidene 8 and (E)-methylidene 34 are almost completely inactive. Reduction of the 18,19-double bond, such as in 39, eliminates the activity, while removal of both of the 19-linked groups such as in heptanor derivative 40 greatly reduces inhibition of the enzyme. (E)-Hexanormethylidene 21 results the first irreversible inhibitor of the series toward the yeast enzyme.

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“…Though these cycloalkenones might be powerful Diels–Alder synthons on paper, the latter two are notoriously sluggish dienophiles. 6–9 …”

Section: Introductionmentioning

confidence: 99%

Intramolecular Diels–Alder Reactions of Cycloalkenones: Translation of High Endo Selectivity to Trans Junctions

Ross

2012

J. Am. Chem. Soc.

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Stereoselective total synthesis of (±)-3-oxosilphinene through intramolecular Diels–Alder reaction

Cited by 15 publications

References 3 publications

100 Years of the Wolff Rearrangement

100 Years of the Wolff Rearrangement

29-Methylidene-2,3-oxidosqualene Derivatives as Stereospecific Mechanism-Based Inhibitors of Liver and Yeast Oxidosqualene Cyclase

Intramolecular Diels–Alder Reactions of Cycloalkenones: Translation of High Endo Selectivity to Trans Junctions

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