16308-15-9Relevant academic research and scientific papers
Remote Substituents as Potential Control Elements for the Solid-State Structures of Hypervalent Iodine(III) Compounds
Li, Guobi,Rheingold, Arnold L.,Protasiewicz, John D.
, p. 7865 - 7875 (2021)
Hypervalent iodine (HVI) compounds are very important selective oxidants often employed in organic syntheses. Most HVI compounds are strongly associated in the solid state involving interactions between the electropositive iodine centers and nearby electr
Direct, easy, and scalable preparation of (diacetoxyiodo)arenes from arenes using potassium peroxodisulfate as the oxidant
Hossain, Md. Delwar,Kitamura, Tsugio
, p. 7889 - 7891 (2006)
The reaction of arenes with potassium peroxodisulfate, elemental iodine, and acetic acid in the presence of concd sulfuric acid, efficiently generates the corresponding (diacetoxyiodo)arenes in good yields, providing an easy, safe, and effective method for preparing (diacetoxyiodo)arenes from arenes and iodine.
New and direct approach to hypervalent iodine compounds from arenes and iodine. straightforward synthesis of (diacetoxyiodo)arenes and diaryliodonium salts using potassium μ-peroxo-hexaoxodisulfate
Hossain, Md. Delwar,Kitamura, Tsugio
, p. 2213 - 2219 (2007)
The reaction of arenes with elemental iodine, acetic acid, and potassium μ-peroxo-hexaoxodisulfate (K2S2O8) in the presence of concentrated sulfuric acid, efficiently generated the corresponding (diacetoxyiodo)arenes in good yields. Diaryliodonium triflates were directly synthesized by reaction of arenes with elemental iodine in good yields by using K2S2O8, AcOH, and TfOH. Diaryliodonium tosylates were also prepared from arenes and elemental iodine by using K 2S2O8, AcOH, H2SO4, and TsOH. The procedure involved mild conditions and a straightforward one-pot synthesis.
Preparation and Synthetic Applicability of Imidazole-Containing Cyclic Iodonium Salts
Antonkin, Nikita S.,Vlasenko, Yulia A.,Yoshimura, Akira,Smirnov, Vladimir I.,Borodina, Tatyana N.,Zhdankin, Viktor V.,Yusubov, Mekhman S.,Shafir, Alexandr,Postnikov, Pavel S.
, p. 7163 - 7178 (2021/05/29)
A novel approach to the preparation of imidazole-substituted cyclic iodonium salts has been developed via the oxidative cyclization of 1-phenyl-5-iodoimidazole using a cheap and available Oxone/H2SO4 oxidative system. The structure of the new polycyclic heteroarenes has been confirmed by single-crystal X-ray diffractometry, revealing the characteristic structure features for cyclic iodonium salts. The newly produced imidazole-flanked cyclic iodonium compounds were found to readily engage in a heterocyclization reaction with elemental sulfur, affording benzo[5,1-b]imidazothiazoles in good yields.
Stereoselective Aminoiodination of Activated Alkynes with Organoiodine(III) Reagents and Amines via Multiple-Site Functionalization: Access to Iodinated Enamines and N-Aryl Indoles
Arepally, Sagar,Chamuah, Ajoy,Katta, Narenderreddy,Sharada, Duddu S.
, p. 1542 - 1547 (2019/02/03)
A stereoselective aminoiodination of activated alkynes with PhI(OAc)2 and amines via multiple-site functionalization to afford (Z)diethyl 2-(diphenylamino)-3-iodomaleate derivatives with superior yields has been described. The key feature of th
The Role of Iodanyl Radicals as Critical Chain Carriers in Aerobic Hypervalent Iodine Chemistry
Hyun, Sung-Min,Yuan, Mingbin,Maity, Asim,Gutierrez, Osvaldo,Powers, David C.
supporting information, p. 2388 - 2404 (2019/09/12)
Selective O2 utilization remains a substantial challenge in synthetic chemistry. Biological small-molecule oxidation reactions often utilize aerobically generated high-valent catalyst intermediates to effect substrate oxidation. Available synthetic methods for aerobic oxidation catalysis are largely limited to substrate functionalization chemistry by low-valent catalyst intermediates (i.e., aerobically generated Pd(II) intermediates). Motivated by the need for new chemical platforms for aerobic oxidation catalysis, we recently developed aerobic hypervalent iodine chemistry. Here, we report that in contrast to the canonical two-electron oxidation mechanisms for the oxidation of organoiodides, the developed aerobic hypervalent iodine chemistry proceeds via a radical chain mechanism initiated by the addition of aerobically generated acetoxy radicals to aryl iodides. Despite the radical chain mechanism, aerobic hypervalent iodine chemistry displays substrate tolerance similar to that observed with traditional terminal oxidants, such as peracids. We anticipate that these insights will enable new sustainable oxidation chemistry via hypervalent iodine intermediates. O2 is routinely utilized in biological catalysis to generate high-valent catalyst intermediates that engage in substrate oxidation chemistry. Analogous synthetic chemistry via aerobically generated high-valent intermediates would enable new sustainable synthetic methods but is largely unknown because of the challenges in selective O2 utilization. We have developed aerobic hypervalent iodine chemistry as a platform for coupling O2 reduction with a diverse set of substrate functionalization mechanisms. Many of the synthetic applications of hypervalent iodine reagents rely on selective two-electron oxidation-reduction chemistry. Here, we report that one-electron oxidation reactions pathways via iodanyl radical intermediates are critical in aerobic hypervalent iodine chemistry. The new appreciation for the critical role that iodanyl radicals can play in the synthesis of hypervalent iodine compounds will provide new opportunities in sustainable oxidation catalysis. Aerobic hypervalent iodine chemistry provides a strategy for coupling the one-electron chemistry of O2 with two-electron processes typical of organic synthesis. We show that in contrast to the canonical two-electron oxidation of aryl iodides, aerobic synthesis proceeds by a radical chain process initiated by the addition of aerobically generated acetoxy radicals to aryliodides to generate iodanyl radicals. Robustness analysis reveals that the developed aerobic oxidation chemistry displays substrate tolerance similar to that observed in peracid-based methods and thus holds promise as a sustainable synthetic method.
SYNTHESIS OF HYPERVALENT IODINE REAGENTS WITH DIOXYGEN
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Paragraph 0073-0075, (2019/01/15)
Methods of synthesis of hypervalent iodine reagents and methods for oxidation of organic compounds are disclosed.
Safer Synthesis of (Diacetoxyiodo)arenes Using Sodium Hypochlorite Pentahydrate
Watanabe, Ayumi,Miyamoto, Kazunori,Okada, Tomohide,Asawa, Tomotake,Uchiyama, Masanobu
, p. 14262 - 14268 (2018/11/23)
A practical method for the preparation of (diacetoxyiodo)arene ArI(OAc)2 is described. The use of commercially available sodium hypochlorite pentahydrate (NaClO·5H2O) enabled safe, rapid, and inexpensive oxidation of iodoarenes with electron-withdrawing and -donating substituents. The method allows tandem divergent access to synthetically useful organo-λ3-iodanes such as hydroxyl(tosyloxy)iodobenzene, iodosylbenzene, iodonium ylide, etc.
Synthesis of 2-Quinolinones via a Hypervalent Iodine(III)-Mediated Intramolecular Decarboxylative Heck-Type Reaction at Room Temperature
Fan, Huaqiang,Pan, Peng,Zhang, Yongqiang,Wang, Wei
supporting information, p. 7929 - 7932 (2019/01/04)
A hypervalent iodine(III)-mediated intramolecular decarboxylative Heck-type reaction of 2-vinyl-phenyl oxamic acids has been developed. The unique ring-strain-enabled radical decarboxylation mechanism is preliminarily revealed. This protocol features metal-free reaction conditions and operational simplicity, allowing the lactamization of 2-vinylanilines using a readily accessible carbonyl source and the synthesis of various 2-quinolinones with excellent chemoselectivity at room temperature.
Oxidase catalysis via aerobically generated hypervalent iodine intermediates
Maity, Asim,Hyun, Sung-Min,Powers, David C.
, p. 200 - 204 (2018/02/06)
The development of sustainable oxidation chemistry demands strategies to harness O'2 as a terminal oxidant. Oxidase catalysis, in which O'2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O'2 reduction. Direct O'2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O'2 and the disparate electron inventories of four-electron O'2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents - a broadly useful class of selective two-electron oxidants - from O'2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O'2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.
