ChemInform Abstract: Catalytic Iodination of Aromatic Compounds via Their ortho‐Palladium Complexes.

Andrienko, O. S.; Goncharov, V. S.; Raida, V. S.

doi:10.1002/chin.199644063

Cited by 3 publications

(3 citation statements)

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“…In 1970 and 1971, Fahey at Phillips Petroleum reported the catalytic chlorination of azobenzene to form a mixture of mono- and polyhalogenation products containing chlorine in the ortho position (eq 27). 91,92 In 1996, Andrienko reported the iodination of azobenzene with I 2 and a combination of PdI 2 and CuCl 2 as catalyst, 93 and in 2001 Kodama filed a patent on the ortho halogenation of a precursor to an agrochemical (vide infra). 25 …”

Section: From Stoichiometric Reactions and Initial Catalytic Reactionmentioning

confidence: 99%

Evolution of C–H Bond Functionalization from Methane to Methodology

2015

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This Perspective presents the fundamental principles, the elementary reactions, the initial catalytic systems, and the contemporary catalysts that have converted C−H bond functionalization from a curiosity to a reality for synthetic chemists. Many classes of elementary reactions involving transition-metal complexes cleave C−H bonds at typically unreactive positions. These reactions, coupled with a separate or simultaneous functionalization process lead to products containing new C−C, C−N, and C−O bonds. Such reactions were initially studied for the conversion of light alkanes to liquid products, but they have been used (and commercialized in some cases) most often for the synthesis of the more complex structures of natural products, medicinally active compounds, and aromatic materials. Such a change in direction of research in C−H bond functionalization is remarkable because the reactions must occur at an unactivated C−H bond over functional groups that are more reactive than the C−H bond toward classical reagents. The scope of reactions that form C−C bonds or install functionality at an unactivated C−H bond will be presented, and the potential future utility of these reactions will be discussed.

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Section: From Stoichiometric Reactions and Initial Catalytic Reactionmentioning

confidence: 99%

Evolution of C–H Bond Functionalization from Methane to Methodology

2015

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“…In analogy to the early reports from Fahey, , Raida and co-workers developed conditions for the catalytic ortho -iodination of azobenzene using PdI 2 and CuCl 2 as catalyst and cocatalyst, repsectively (Scheme ). It was noted that the Pd/Cu ratio as well as the chloride ion concentration affected the overall reaction rate, and lower values of both led to increased reaction efficiency. In contrast to recent results, the iodination of acetanilide was unsuccessful, which may be a result of a difficult ortho -palladation of this compound with PdCl 2 .…”

Section: Synthesis Of Aryl and Heteroaryl Halidesmentioning

confidence: 99%

Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation

2016

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The high utility of halogenated organic compounds has prompted the development of a vast number of transformations which install the carbon-halogen motif. Traditional routes to these building blocks have commonly involved multiple steps, harsh reaction conditions, and the use of stoichiometric and/or toxic reagents. In this regard, using transition metals to catalyze the synthesis of organohalides has become a mature field in itself, and applying these technologies has allowed for a decrease in the production of waste, higher levels of regio- and stereoselectivity, and the ability to produce enantioenriched target compounds. Furthermore, transition metals offer the distinct advantage of possessing a diverse spectrum of mechanistic possibilities which translate to the capability to apply new substrate classes and afford novel and difficult-to-access structures. This Review provides comprehensive coverage of modern transition metal-catalyzed syntheses of organohalides via a diverse array of mechanisms. Attention is given to the seminal stoichiometric organometallic studies which led to the corresponding catalytic processes being realized. By breaking this field down into the synthesis of aryl, vinyl, and alkyl halides, it becomes clear which methods have surfaced as most favored for each individual class. In general, a pronounced shift toward the use of C-H bonds as key functional groups, in addition to methods which proceed by catalytic, radical-based mechanisms has occurred. Although always evolving, this field appears to be heading in the direction of using starting materials with a significantly lower degree of prefunctionalization in addition to less expensive and abundant metal catalysts.

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“…Palladium catalysis offers a powerful tool for the halogenation of hydrocarbons, and it has been explored for the iodination of arenes and aliphatic hydrocarbons . Yet, a palladium-catalyzed C–H iodination of olefins has not been documented.…”

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confidence: 99%