The vinylarene Diels-Alder reaction, development and potential

Andrus, Merritt B.; Saavedra, Diana I.

doi:10.1016/j.tet.2019.02.039

Cited by 12 publications

(10 citation statements)

References 102 publications

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“…Notwithstanding the fact that the scope of this review does not cover the latest data on the IMDA cyclization of linear dienes 625 into adducts 626 (see Scheme 176 and the review 2h devoted to this subject, as well as the most notable recent papers in the field 12 63 116 ), it includes and demonstrates the latest achievements in the field of Diels–Alder reactions of vinylarenes as well as aryl acetylenes. Exhaustive information is also provided regarding its synthetic possibilities, including numerous examples of the preparation of naturally occurring compounds and physiologically active substances by utilizing the IMDAV reaction as a the key step.…”

Section: Discussionmentioning

confidence: 99%

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IntraMolecular Diels–Alder Reactions of Vinylarenes and Alkynyl Arenes (the IMDAV Reaction)

Krishna¹,

Grudinin²,

Nikitina³

et al. 2021

Synthesis

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This comprehensive review summarizes the published literature data concerning the intramolecular Diels–Alder reactions of vinylarenes (the IMDAV reaction) and alkynyl arenes from 1970 to 2019, and covers mainly intramolecular [4+2] cycloaddition reactions of vinyl- or acetylene-substituted furans, thiophenes, pyrroles, indoles, imidazoles, benzenes, and naphthalenes, in which the unsaturated substituent is linked directly to an arene moiety. The selected area of the Diels–Alder reaction differs from other forms of [4+2] cycloadditions due to the uniqueness of the diene fragment, which, along with an exocyclic multiple bond, includes the double bond of an aromatic or heteroaromatic nucleus in its system. Thus, during the formation of the [4+2] cycloaddition intermediate, the aromaticity of furan, thiophene and even benzene rings is broken, leading, as a rule, to the formation of heterocyclic structures rarely accessible by other methods, in contrast to the majority of intermolecular Diels–Alder reactions, with the highest degree of chemo-, regio-, and diastereoselectivity. Therefore, the IMDAV approach is often used for the synthesis of naturally occurring and bioactive molecules, which are also discussed in this review alongside other applications of this reaction. Whenever possible, we have tried to avoid examples of radical, photochemical, oxidative, precious-metal-complex-catalyzed cyclizations and other types of formal [4+2] cycloadditions, focusing on thermal Diels–Alder reactions in the first step, according to the classical mechanism. The second stage of the process, aromatization, is unique for many initial substrates, and hence considerable attention in this overview is given to the detailed description of the reaction mechanisms.1 Introduction2 IMDAV Reactions of Vinylfurans2.1 Alkenes as Internal Dienophiles2.2 Alkynes and Allenes as Internal Dienophiles3 IMDAV Reactions of Vinylthiophenes3.1 Alkenes as Internal Dienophiles3.2 Alkynes as Internal Dienophiles4 IMDAV Reactions of Vinylbenzothiophenes5 IMDAV Reactions of Vinylpyrroles6 IMDAV Reactions of Vinylindoles6.1 Alkenes as Internal Dienophiles6.2 Alkynes as Internal Dienophiles7 IMDAV Reactions of Styrenes and Vinylnaphthalenes7.1 Alkenes as Internal Dienophiles7.2 Alkynes as Internal Dienophiles7.3 Alkynes as Internal Dienophiles in Aryl Acetylenes (the Intramolecular Dehydro Diels–Alder Reaction)8 IMDAV Reactions of Vinylimidazoles, Vinylisoxazoles and Vinylpyridines9 Conclusion10 Abbreviations

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Section: Discussionmentioning

confidence: 99%

“…The most interesting examples and synthetic applications of the IMDA reaction to natural product synthesis have already been summarized in a significant number of reviews, the most recent of which can be found in the literature. 2` b c d e f g h…”

Section: Introductionmentioning

confidence: 99%

IntraMolecular Diels–Alder Reactions of Vinylarenes and Alkynyl Arenes (the IMDAV Reaction)

Krishna¹,

Grudinin²,

Nikitina³

et al. 2021

Synthesis

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“…With the three substrates in hand, the intramolecular Diels− Alder reaction was initially investigated using microwave (μW) conditions. 4 Different solvents, including nitrobenzene, acetic anhydride, acetonitrile, benzene, and toluene, were used at 10 °C above their boiling points under sealed tube conditions. Lewis acid additives [copper(II) triflate, ZnCl 2 ] were also explored.…”

Section: ■ Introductionmentioning

confidence: 99%

“…[α] D20 (c = 0.0475, CH 2 Cl 2 ) + 2.6; TLC R f (EtOAc/Hex 4:1) 0.21; 1 H NMR (500 MHz, CDCl 3 ): δ 7.41 (d, J = 7 4. Hz, 2H), 67.31 (m, 7H), 7.21 (d, J = 7.1 Hz, 2H), 7.03 (d, J = 15.5 Hz, 1H),6.71 (d, J = 15.9 Hz, 1H),6.33 (dt, J = 15.9 Hz, 1H), 4.90 (dd, J = 6.5 Hz, 2H), 4.75 (m, 1H), 4.25 (ddd, 1H), 3.35, (dd, J = 13.5 Hz, 1H), 2.83 (dd, J = 13 5.…”

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confidence: 99%

Intramolecular Heteroatom and Styryl Diels–Alder Reactions, Asymmetric Cycloadditions of Chiral 3-Phenylallyl Maleic Esters

Mpaata,

Miller,

Bonsrah

et al. 2024

J. Org. Chem.

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Polycyclic aryl naphthalene and tetralin dihydro arylnaphthalene lactone lignans possess anticancer and antibiotic activity. Related furo [3,4-c]pyranones, typified by the sequester-terpenoid isobolivianine, show similar antiproliferative bioactivity. Efficient syntheses of compounds featuring these polycyclic cores have proven challenging due to low yields and poor stereoselectivity. We report the synthesis of chiral cinnamyl but-2-enanoates and 3,3-diphenylallyl-but-2-enoates 1 as new Diels− Alder substrates. These compounds undergo [4 + 2]-cycloadditions to give furo[3,4-c]pyranones 2 in good yield (70%) and diastereoselectivity (7:1), together with naphthyl 3 and dihydronaphthyl tetralins 4 as minor products. Molecular structures and stereochemistries of the major products were verified using X-ray diffraction. Density functional theory calculations revealed that the cycloaddition process involves a bispericyclic/ambimodal process where there is a single transition state that leads to both intramolecular styryl Diels−Alder (ISDA) 3, 4 and intramolecular hetero Diels−Alder (IHDA) cycloadducts 2. With the elevated temperature conditions after cycloaddition, the resulting ISDA cycloadduct either undergoes [3,3]-sigmatropic rearrangement to the more stable major IHDA product or aromatization leading to the phenyltetralin.

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“…The six-membered cycles, including the carbocycle and heterocycle, are commonly the key architectures embedded in various biologically and pharmaceutically active products [1][2][3]. Occurring as a concerted process, the Diels-Alder reaction is by far the best known and most widely applied [4][5][6][7][8][9][10][11][12][13][14] synthetic strategy. The [3 + 3]cycloaddition/annulation, which works as an important complementary, offers potential alternatives and tends to undergo the stepwise mechanism due to the symmetry disallowance [15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Mechanism of the phosphine‐catalyzed [3 + 3] annulation with MBH carbonates as the potential dipoles

Chen

Liu

et al. 2022

J of Physical Organic Chem

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The [3 + 3] cylcloaddition/annulation is an important complementary for construction of six‐membered ring. With addition of organophosphine to the Morita‐Baylis‐Hillman (MBH) carbonate, a potential C3 synthon can be furnished. In this work, the catalytic mechanisms for using this synthon as the nucleophilic or electrophilic dipole to react with the cyclohexa‐2,5‐dienone‐substituted benzenesulfonamide are studied by the density functional theory method. The computational results reveal that the nucleophilic addition of the amide anion to the allylic phosphonium is more favorable than the electrophilic addition of alkenyl in the benzenesulfonamide with the allylic phosphorus ylide. Namely, the allylic phosphonium adduct, rather than the allylic phosphorus ylide that is generated by deprotonation of the allylic phosphonium, is more likely to act as the potential dipole. The global reactivity index calculations indicate that species involved in the favored pathway have better reactivities (both in nucleophilicity and electrophilicity), especially the significantly higher nucleophilicity of the amide anion.

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The vinylarene Diels-Alder reaction, development and potential

Cited by 12 publications

References 102 publications

IntraMolecular Diels–Alder Reactions of Vinylarenes and Alkynyl Arenes (the IMDAV Reaction)

IntraMolecular Diels–Alder Reactions of Vinylarenes and Alkynyl Arenes (the IMDAV Reaction)

Intramolecular Heteroatom and Styryl Diels–Alder Reactions, Asymmetric Cycloadditions of Chiral 3-Phenylallyl Maleic Esters

Mechanism of the phosphine‐catalyzed [3 + 3] annulation with MBH carbonates as the potential dipoles

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