Cycloaddition reactions. Addition of dimethyl acetylenedicarboxylate to 1-dimethylaminoindene

Doyle, Terrence W.

doi:10.1139/v70-269

Cited by 5 publications

(1 citation statement)

References 5 publications

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“…These results and the fact that the photochemical ring opening of cyclobutenes is well-precedented 12 prompted us to explore the photolysis of the cyclobutenes 3 , 4 , 6 , and 7 . To the best of our knowledge, the photolytic ring opening of cyclobutenes condensed to the diquinane moiety has seldom been used as a synthetic approach to hydroazulene skeletons . Our first experiments were performed in a Pyrex photoreactor with a medium-pressure Hg lamp (125 W).…”

Section: Resultsmentioning

confidence: 99%

Photochemical, Thermal, and Base-Induced Access to Hydroazulene Derivatives via Two-Carbon Ring-Enlargement Reactions of Condensed Electrophilic Cyclobutenes

Mislin

Miesch

2002

J. Org. Chem.

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Enamines, silyl enol ethers, and beta-keto ester anions derived from bicyclo[3.3.0]octan-2-one efficiently underwent a formal [2 + 2] cycloaddition reaction with DMAD and ethyl propynoate leading to a large variety of electrophilic cyclobutenes. The latter were transformed into polyfunctionalized bicyclo[5.3.0]decane (or hydroazulene) ring systems in high yields by fragmentation of the cyclobutene moiety. These two-carbon ring-enlargement reactions were utilized as a synthetic tool for the construction of a polyfunctionalized hydroazulene derivative that represents a potential precursor of the tricyclic framework of ingenol.

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Section: Resultsmentioning

confidence: 99%

Photochemical, Thermal, and Base-Induced Access to Hydroazulene Derivatives via Two-Carbon Ring-Enlargement Reactions of Condensed Electrophilic Cyclobutenes

Mislin

Miesch

2002

J. Org. Chem.

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Expansion to Seven-Membered Rings

2000

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Synthesis of pyrrolizines by intramolecular capture of 1,4-dipolar intermediates in reactions of enamines with dimethyl acetylenedicarboxylate

et al. 1981

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Solvent polarity and reaction temperature strongly influence the reactions of dimethyl acetylenedicarboxylate (DMAD) with I-pyrrolidinyl enamines of acyclic and cyclic ketones. Whereas DMAD and I-[l-phenylt-@henylthio)ethenyl]pyrrolidiae (3) give only a mixture of the isomeric I$-butadiencs (5) in apolar solvents, in methanol the main product is the pyrrolizine 7, together with 5. Again in methanol, DMAD reacts at 0-Y with 8.9 and 10 to give exclusively I : I adducts, tbe pyrrolizines 11, 12 and 13, respectively, whereas at-50" 8 and 9 give I : 2 (enamine : DMAD) adducts. the pyrrolixines 14 and 15, respectively; a siqle crystal X-ray analysis of 14 gave the structure of the I : 2 adducta. In the same solvent methyl propiolate and 8 give only the linear Michael adduct 17. The enamine-ketone 18 reacts with DMAD in propylene carbonate at W' to give, via (2 t Zj-cycloaddition and ring expansion, 19, and the linear Michael adduct 20. The mechanism of (2 t Zj-cycloaddition and pyrrolizine formation is discussed in terms of a common tied-ion pair intermediate formed in the first. ratedetermining step,

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Cycloaddition reactions. Addition of dimethyl acetylenedicarboxylate to 1-dimethylaminoindene

Cited by 5 publications

References 5 publications

Photochemical, Thermal, and Base-Induced Access to Hydroazulene Derivatives via Two-Carbon Ring-Enlargement Reactions of Condensed Electrophilic Cyclobutenes

Photochemical, Thermal, and Base-Induced Access to Hydroazulene Derivatives via Two-Carbon Ring-Enlargement Reactions of Condensed Electrophilic Cyclobutenes

Expansion to Seven-Membered Rings

Synthesis of pyrrolizines by intramolecular capture of 1,4-dipolar intermediates in reactions of enamines with dimethyl acetylenedicarboxylate

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