Cycloaddition reactions of phthalimide substituted cyclic polyenes with heteroatom dienophiles

Templin, Stephen S.; Wallock, Nathaniel J.; Haworth, Daniel T.; Donaldson, William A.; Bennett, Dennis W.; Siddiquee, Tasneem A.

doi:10.1002/jhet.5570440334

Cited by 8 publications

(8 citation statements)

References 40 publications

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“…The treatment of (±)‐ 7 with singlet oxygen gave (±)‐ 8 as a single diastereomer (Scheme ). The relative stereochemistry of 8 was tentatively assigned on the basis of that previously observed for the products of 7 with arylnitroso dienophiles 9. This tentative assignment was eventually corroborated on the basis of further reactions.…”

Section: Resultssupporting

confidence: 56%

“…The relative stereochemistry of 8 was tentatively assigned on the basis of that previously observed for the products of 7 with arylnitroso dienophiles. 9 This tentative assignment was eventually corroborated on the basis of further reactions. Reduction of 8 with zinc in acetic acid gave the enediol (±)-9.…”

Section: Resultsmentioning

confidence: 78%

“…Purification of the residue by column chromatography (SiO2, CH2Cl2/MeOH gradient=19:1→9:1) gave recovered (±)-18 (26 7, 133.4, 124.4, 78.2 (br), 76.6, 68.6 (br), 50.4, 20.2, 18.5, 9. 17 (ddt,J=3.1,6.3,9.2 Hz,1 H;0.90 (q,J=6.3 Hz,1 H;0.80 ppm (td,J=6.1,9.1 Hz, 1 H; H8exo); 13 C NMR (100 MHz,CD3OD): δ=168.5,133.8,132.0,122.6,73.2,71.5,68.1,65.7,51.9,17.7,16.7,6.3 ppm; elemental analysis calcd (%) for C16H17NO6: C 60. 18, H 5.36; found: C 59.97, H 5.36.…”

Section: Chemistry a European Journalmentioning

confidence: 99%

“…5.55 (ddd,J=2.0,5.2,12.8 Hz,1 H;C CH),5.43 (ddd,J=2.0,3.6,12.8 Hz,1 H;C CH),1 H;1 H;2.41 (d,J=8.4 Hz,1 H;OH),2.25 (d,J=3.6 Hz,1 H;OH),1.48 (tt,J=6.7,9.1 Hz, 1 H; H-7), 1.22-1.14 (m, 1 H; H-1), 1.08 (q, J=5.9 Hz, 1 H; H-8endo), 0.83 ppm (dt, J=5.9, 8.7 Hz, 1 H; H-8exo); 13 C NMR (100 MHz,CDCl3): δ=168.0,134.3,132.2,128.6,127.2,123.5,73.0,71.9,48.7,17.9,16.5,7.2 2 H;Phth),2 H;Phth),6.16 (dd,J=5.8,11.8 Hz,1 H;5.65 (dd,J=7.6,12.0 Hz,1 H;5.25 (dd,J=4.0,10.4 Hz,1 H;2 H; …”

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confidence: 99%

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Generation of Molecular Complexity from Cyclooctatetraene: Preparation of Aminobicyclo[5.1.0]octitols

El‐Mansy

Flister

Lindeman

et al. 2015

Chemistry A European J

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A series of eight stereoisomeric N-(tetrahydroxy bicyclo-[5.1.0]oct-2S*-yl)phthalimides were prepared in one to four steps from N-(bicyclo[5.1.0]octa-3,5-dien-2-yl)phthalimide (±)-7, which is readily available from cyclooctatetraene (62 % yield). The structural assignments of the stereoisomers were established by 1 H NMR spectral data as well as X-ray crystal structures for certain members. The outcomes of several epoxydiol hydrolyses, particularly ring contraction and enlargement, are of note. The isomeric phthalimides as well as the free amines did not exhibit β-glucosidase inhibitory activity at a concentration of less than 100 μM.

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Section: Resultssupporting

confidence: 56%

Section: Resultsmentioning

confidence: 78%

Section: Chemistry a European Journalmentioning

confidence: 99%

mentioning

confidence: 99%

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Generation of Molecular Complexity from Cyclooctatetraene: Preparation of Aminobicyclo[5.1.0]octitols

El‐Mansy

Flister

Lindeman

et al. 2015

Chemistry A European J

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“…The hetero-Diels–Alder reactions of both N -phenyl-1,2,4-triazolin-3,5-dione (PTAD) and nitrosobenzene with all three cyclic dienes, however, occur readily under mild conditions, as shown in Scheme . − …”

Section: Introductionmentioning

confidence: 99%

Theoretical Analysis of Reactivity Patterns in Diels–Alder Reactions of Cyclopentadiene, Cyclohexadiene, and Cycloheptadiene with Symmetrical and Unsymmetrical Dienophiles

Levandowski

Houk

2015

J. Org. Chem.

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The Diels-Alder reactions of cyclopentadiene, cyclohexadiene, and cycloheptadiene with a series of dienophiles were studied with quantum mechanical calculations (M06-2X density functional theory) and analyzed with the distortion/interaction model. The poor reactivities of cyclohexadiene and cycloheptadiene with dienophiles that give relatively synchronous transition states result from the substantial distortion required to achieve a transition state involving the formation of two bonds of the diene simultaneously. However, highly asynchronous or stepwise reactions result in less distortion of the diene and less differences in reactivities of different dienes. The transition state geometry of cyclopentadiene is less distorted in the asynchronous reaction with 1,1-dicyanoethylene compared to that with cis- and trans-1,2-dicyanoethylenes, which react through synchronous transition states.

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Development of Domino Processes by Using 7‐Silylcycloheptatrienes and Its Analogues

Beniazza

Desvergnes

Girard

et al. 2012

Chemistry A European J

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7-Silyl- and 7-silylmethylcycloheptatrienes were shown to react with acylnitroso reagents at room temperature, through their norcaradiene forms, to generate the corresponding cycloadducts 5 a-b and 6 a-b as single diastereomers. The course of the reaction was dramatically modified by changing the reaction conditions. Using a polar medium, functionalized cyclohexa-1,3-dienes 7 a-b and bicyclic compounds 13 a-b were instead generated, incorporating one or two amino groups. Similar behavior was observed by using other dienophiles, including triazolinedione, but also activated aldehydes and ketones. A tentative mechanism has been proposed to rationalize the formation of both classes of products that relies on a domino process involving four consecutive elementary steps, in this order: 1) electrocyclic process, 2) hetero-Diels-Alder reaction, 3) cyclopropane ring opening, and 4) hetero-Diels-Alder reaction. Trapping of the cationic intermediate and isolation of the primary cycloadduct provide support for this hypothesis. An enantioselective version of the cascade using cycloheptatriene 4 b and aldehydes and ketones, under copper(II) catalysis was also carried out, leading to cyclohexa-1,3-dienes 21, 28, and 30 with enantioselectivities up to 93 % ee. Finally, elaboration of the intermediates above has been carried out, opening a straightforward access to sugar mimics 42-43 and complex polycyclic systems 36 and 39.

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Cycloaddition reactions of phthalimide substituted cyclic polyenes with heteroatom dienophiles

Cited by 8 publications

References 40 publications

Generation of Molecular Complexity from Cyclooctatetraene: Preparation of Aminobicyclo[5.1.0]octitols

Generation of Molecular Complexity from Cyclooctatetraene: Preparation of Aminobicyclo[5.1.0]octitols

Theoretical Analysis of Reactivity Patterns in Diels–Alder Reactions of Cyclopentadiene, Cyclohexadiene, and Cycloheptadiene with Symmetrical and Unsymmetrical Dienophiles

Development of Domino Processes by Using 7‐Silylcycloheptatrienes and Its Analogues

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