Synthesis and properties of azuleno[2,1-a]-3-8-methano[ 10 ] annulene and its 2-methyl derivative
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Cited by 12 publications
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The McMurry coupling reaction has been recognized as one of the most efficient methods for the synthesis of alkenes from carbonyl compounds. This reaction can be applied to the preparation of various alkenes that are otherwise difficult to prepare. For example, sterically congested tetrasubstituted alkenes as well as medium to large membered rings involving natural products may be accessed via this process. This coupling utilizes various low‐valent titanium reagents generated by the reduction of titanium (III or IV) chloride with K, Zn, LiAlH 4 , C 8 K, amongst others. Furthermore, a variety of low‐valent metal species other than titanium, including aluminum, zirconium, niobium, molybdenum, indium, tungsten, and samarium, have also been found to promote the reductive coupling of carbonyl compounds. The scope and limitations of these reagent systems are reviewed in this chapter, together with the stereochemistry and reaction mechanism. This reaction is categorized into four coupling modes: i) homocoupling giving symmetrical alkenes, ii) mixed coupling giving unsymmetrical alkenes, iii) intramolecular coupling giving cycloalkenes, and iv) tandem coupling giving cyclic polyenes. Characteristics of these reaction modes are described briefly. A selection of synthetic applications are reviewed, including examples of the preparation of sterically congested and strained alkenes, medium to large‐ring compounds, biologically active targets, as well as substrates applicable in material science. Experimental conditions used for this versatile process are summarized to assist the choice of suitable conditions.
The McMurry coupling reaction has been recognized as one of the most efficient methods for the synthesis of alkenes from carbonyl compounds. This reaction can be applied to the preparation of various alkenes that are otherwise difficult to prepare. For example, sterically congested tetrasubstituted alkenes as well as medium to large membered rings involving natural products may be accessed via this process. This coupling utilizes various low‐valent titanium reagents generated by the reduction of titanium (III or IV) chloride with K, Zn, LiAlH 4 , C 8 K, amongst others. Furthermore, a variety of low‐valent metal species other than titanium, including aluminum, zirconium, niobium, molybdenum, indium, tungsten, and samarium, have also been found to promote the reductive coupling of carbonyl compounds. The scope and limitations of these reagent systems are reviewed in this chapter, together with the stereochemistry and reaction mechanism. This reaction is categorized into four coupling modes: i) homocoupling giving symmetrical alkenes, ii) mixed coupling giving unsymmetrical alkenes, iii) intramolecular coupling giving cycloalkenes, and iv) tandem coupling giving cyclic polyenes. Characteristics of these reaction modes are described briefly. A selection of synthetic applications are reviewed, including examples of the preparation of sterically congested and strained alkenes, medium to large‐ring compounds, biologically active targets, as well as substrates applicable in material science. Experimental conditions used for this versatile process are summarized to assist the choice of suitable conditions.
Dehydrogenation Dehydrohalogenation and Elimination of Alkyl Halides 1,1‐Dihalides 1,2‐Dihalides 1,3‐Dihalides Trihaloalkanes β‐Halo Ethers Halohydrins Halo Aldehydes and Ketones Halo Carboxylic Acids Halo Esters β‐Halo Sulfonates Amines β‐Halo Amines and Derivatives Amine Oxides (Cope Elimination) Quaternary Ammonium Salts N ‐Alkyl‐ N , N ‐Disulfonimides N ‐Nitrosocarboxamides Nitro Compounds Diazo Compounds β‐Substituted Azides Ethers β‐Substituted Ethers Sulfides α‐Halosulfides β‐Halosulfides β‐Hydroxysulfides Sulfoxides β‐Alkoxy‐ and Hydroxy‐Sulfoxides Sulfones α‐Halosulfones (Ramberg—Bäcklund Reaction) β‐Hydroxysulfones β‐Acyloxysulfones Other β‐Substituted Sulfones Disulfones Sulfonyl Halides β‐Oxyselenides Selenoxides Tellurides Organosilanes β‐Halosilanes β‐Oxysilanes and ‐Stannanes β‐Aminosilanes Dehydration of Alcohols Sulfonate Esters Sulfates Phosphates and Thiophosphates Xanthates Thiocarbonates Carbamates N ‐Methyl‐4‐alkoxypyridinium Iodides 1,2‐Diols and Derivatives 1,2‐Disulfonates 1,3‐Diols Acetals Dithioacetals Aldehydes and Ketones Lactols Carboxylic Acids Acid Halides Acid Anhydrides Esters and Lactones Amides and Lactams Nitriles Miscellaneous Reactions
Ethynylated 2H-cyclohepta[b]furan-2-ones 5-15 have been prepared by Pd-catalyzed alkynylation of 3-iodo-5-isopropyl-2H-cyclohepta[b]furan-2-one (2) with the corresponding ethynylarenes or the reaction of 2-iodothiophene with 3-ethynyl-5-isopropyl-2H-cyclohepta[b]furan-2-one (4) under Sonogashira-Hagihara conditions. Compounds 5-15 reacted with tetracyanoethylene in a formal [2+2] cycloaddition reaction, followed by ring opening of the initially formed [2+2] cycloadducts, cyclobutenes, to afford the corresponding 1,1,4,4-tetracyanobutadienyl (TCBD) chromophores 16-26 in excellent yields. The intramolecular charge-transfer interactions between the 2H-cyclohepta[b]furan-2-one ring and TCBD acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel TCBD derivatives 16-26 was examined by cyclic voltammetry and differential pulse voltammetry, which revealed multistep electrochemical reduction properties, depending on the number of TCBD units in the molecule. Moreover, a significant color change was observed by UV/Vis spectroscopy under electrochemical reduction conditions.
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