Alkynes in Cycloadditions.
Title:
Alkynes in Cycloadditions.
Author:
Maretina , Irina A.
ISBN:
9781118709337
Personal Author:
Edition:
1st ed.
Physical Description:
1 online resource (312 pages)
Contents:
Alkynes in Cycloadditions -- Contents -- Preface -- Acknowledgments -- Biography -- 1 Introduction -- 2 Regioselective Syntheses of Polysubstituted Benzenes Catalyzed by Transition Metal Complexes -- 2.1 [2+2+2] Cycloaddition Reactions of Acetylenes -- 2.1.1 Reactions of Alkynes with Metallocyclopentadiene as an Intermediate -- 2.1.2 Intra-intermolecular [2+2+2] Cycloaddition of Alkynes -- 2.2 Stereochemical Aspect of Intramolecular and Intermolecular Reactions of Diynes with Monoalkynes -- 2.2.1 Strategy of Enantioselective [2+2+2] Cycloaddition -- 2.3 Heteroatom Bound to the Triple Bond -- 2.3.1 Nitrogen-Containing Substrates -- 2.3.2 [2+2+2] Cycloadditions of Alkynes to Nitriles: Synthesis of Pyridines -- 2.4 Heterohelicens. Asymmetric Syntheses -- 2.4.1 Oxygen-Containing Helicens -- 2.4.2 Nitrogen-Containing Helicens. Helical Dications -- 2.5 Aromatic Rings with Boron and Silicon Substituents -- 2.6 [2+2+2] Cycloaddition Reactions of 1-Alkynylphosphines and Their Derivatives -- 2.7 Intramolecular [2+2+2] Cycloaddition of Diynes to Alkenes -- 2.7.1 Allene as an Alkene Component -- 2.7.2 Formation of Polycyclic Cyclohexadienes by Ru-catalyzed Cascade Reactions of 1,6-Diynes and Alkenes -- 2.7.3 Stereochemical Aspects of the Reaction of Diynes with Alkenes -- 2.7.4 Hetero-[2+2+2] Cycloaddition of Alkynes to Compounds with a Multiple Carbon-Heteroatom Bond -- 2.8 Reactions of [4+2] Cycloaddition and Other Approaches to the Synthesis of Polysubstituted Benzenes -- 2.8.1 Reactions of Conjugated Enynes -- 2.8.2 Acceleration of Pd-catalyzed [4+2]-Benzannulation in the Reaction of Enynes and Diynes in the Presence of Lewis Acids and Bronsted Bases -- 2.9 Combined Reactions -- 2.9.1 Formal [4+2+2] Cycloaddition of 1,6-Diynes to 1,3-Dienes Catalyzed by Ru: Formation of Cyclooctatrienes and Vinylcyclohexadienes.
2.9.2 Formation of Eight-Membered Ring Systems by [4+2+2] Annulation -- 2.9.3 AuBr3 (AlCl3)- and Cu(OTf)2-Catalyzed [4+2] Cycloaddition of Alkynyl- and Alkenyl-Enynones and Enynals: An Approach to Functionalized Polycyclic Hydrocarbons -- 2.10 Construction of Polycyclic Systems -- 2.10.1 Strategies for the Synthesis of Steroid Systems by Co-catalyzed [2+2+2] Cycloaddition of Nonconjugated Enyne-Allenes and Enediynes -- 2.10.2 Cobalt(I)-Mediated [2+2+2] Cyclization of Allene-Diynes: A Diastereoselective Approach to 11-aryl Steroid Core. 11-Aryl-Substituted Steroid Systems by Co-catalyzed [2+2+2] Cyclization of Allene-Diynes -- 2.10.3 Synthesis of (3S)-hydroxyandrosta-5,7-diene-17-ones via Intramolecular Cobalt-Mediated [2+2+2] Cycloaddition -- 2.10.4 Intramolecular Cycloaddition of Nonconjugated Enediynes of a Higher Order as a Route to Functionalized Condensed Polycyclic Systems -- 2.10.5 A Strategy for the Synthesis of Aromatic Molecular-Bowl Hydrocarbons -- 2.10.6 A Route to Archimedenes: Total Synthesis of C3h-symmetric [7]phenylenes -- 2.10.7 Polycyclic Azaheterocycles -- 3 Radical Cycloaromatization of Systems Containing (Z)-3-hexene-1,5-diynes and (Z)-1,2,4-heptatrien-6-ynes and Related Heteroatomic Blocks -- 3.1 The Historical Aspect of the Chemistry of Enediynes, Enyne-Allenes and Enyne-Cumulenes -- 3.1.1 Anticancer Enediyne Antibiotics -- 3.2 Routes to the Cycloaromatization of Enediyne and Enyne-Allene Systems. Bergman and Myers-Saito Cyclization -- 3.2.1 Generation of Free Radicals by (Z)-3-hexene-1,5-diynes and (Z)-1,2,4 heptatrien-6-ynes -- 3.2.2 Thermal Cyclization -- 3.2.3 Photochemical Cyclization -- 3.2.4 Catalytic Cyclization -- 3.3 Cycloaromatization by C1-C5, C2-C7 and C2-C6 (Myers-Saito and Schmittel) Routes to Indeno-Fused Structures -- 3.3.1 Thermal C1-C5 Radical Cyclization of Enediynes.
3.3.2 The Limitations of the Cycloaromatization Reactions -- 3.3.3 Thermal and Photochemical C2-C6 Cyclization of Enyne-Allenes: Switching the Regioselectivity from C2-C7 (Myers-Saito) to C2-C6 (Schmittel) Cyclization Mode -- 3.3.4 Practical Aspects of Syntheses Based on Enyne-Allenes -- 3.4 External Initiation of Enediyne Cycloaromatization -- 3.4.1 Cycloaromatization Initiated by External Radicals -- 3.4.2 Ionic Activation of Cyclization of Enediynes -- 3.4.3 Other Types of Cyclization -- 3.5 Features of Cycloaromatization of Heteroatomic Enediynes -- 3.5.1 Trigger Mechanisms for the Cycloaromatization of Enediynes -- 3.5.2 Nitrogen-Containing Enediynes -- 3.5.3 Metal-Induced Bergman Cycloaromatization -- 3.5.4 Sulfur-Containing Enediynes -- 3.6 Cycloaromatization of Hetero-Systems -- 3.6.1 Enyne-Heteroallene and Enyne-(hetero)cumulenes -- 3.6.2 Features of Dienyne Cyclizations -- 4 Selected Cycloaddition and Heterocyclization Reactions with Unusual Acetylenic and Allenic Starting Compounds -- 4.1 Cycloaddition and Heterocyclization Reactions of Acetylenic Compounds with Electron-Withdrawing Substituents -- 4.2 Diels-Alder [4+2] Cycloaddition: Acetylenes as Dienophiles -- 4.3 Formation of Cyclobutene Derivatives by [2+2]-Cycloaddition -- 4.4 [2+2] Cyclization of Some 1,3-Butadienes Produced from Acetylenic Alcohols of the Propargyl Type -- 4.5 Heterocyclization of Electron-Deficient Acetylenes with Nucleophilic Reagents -- 5 Concluding Remarks -- References -- Index.
Abstract:
Acetylene systems present a new route to cyclic compounds as an alternative to more traditional methods employed in classical organic chemistry. The synthesis of cyclic structures based on acetylene systems has important applications in the formation of nanostructures, naturally occurring compounds and chemosensory materials for the design of nonlinear optics, electronic and photonic devices. Alkynes in Cycloadditions presents a modern review of regioselective synthesis of aromatic and non-aromatic carbocyclic and heterocyclic ring systems based primarily on [2+2+2] and [4+2] cycloadditions, and other reactions of acetylenic units including enediynes and enyne-allenes. Topics covered include: New strategies for the formation of aromatic and polynuclear hydrocarbons based on (Z)-hex-3-en-1,5-diyne and (Z)-hepta-1,2,4-triene-6-yne blocks. One-step synthesis of benzene derivatives, β-substituted naphthalenes and acenes by the cycloaromatization of enediynes and enyne-allenes by Bergman, Myers-Saito and Shmittel. Mechanisms of cycloaromatization resulting in the formation of fulvene and indene systems. Heterocyclization involving enyne-carbodiimides. New achievements in classical cycloaddition reactions such as the Diels-Alder condensation with acetylenic dienophiles and [2+2] cycloadditions with acetylene components Alkynes in Cycloadditions presents a comprehensive summary of the literature on methods for the synthesis of ring systems from acetylenes for academic researchers working in the fields of organic synthesis, physical organic chemistry, organometallic chemistry, catalysis, materials science, nanomaterials and biochemistry.
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Electronic reproduction. Ann Arbor, Michigan : ProQuest Ebook Central, 2017. Available via World Wide Web. Access may be limited to ProQuest Ebook Central affiliated libraries.
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