{"title":"The Chemistry of Nitroso Oxides","authors":"E. Chainikova, S. Khursan, R. Safiullin","doi":"10.1002/9780470682531.PAT0828","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0828","url":null,"abstract":"Nitroso oxides (RNOO) are the isoelectronic analogs of carbonyl oxides (R2COO) and ozone (O3) and, as well as these species, possess a three-centered 4π-electron system, which determines their chemical properties and reactivity unusual for a family of peroxides. The review is focused on the chemistry of the parent nitroso oxide (HNOO) and its aromatic analogs (ArNOO). The structure, spectral properties, methods for generation, reactivity and mechanisms of various transformations of these species both in the gas and condensed media are discussed in detail. An aromatic substituent significantly stabilizes the π-system of nitroso oxide. The typical reactions of nitroso oxides are O-transfer to an appropriate substrate or [3+2]-cycloaddition to unsaturated bonds. Special attention was paid to the redox isomerization of arylnitroso oxides with ring cleavage that leads to the formation of diene nitrile oxides. \u0000 \u0000 \u0000Keywords: \u0000 \u0000aromatic azides; \u0000mechanism of reactions; \u0000nitrenes; \u0000nitroso oxides; \u0000photooxidation; \u0000reactive intermediates","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"45 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2014-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91165428","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"The Chemistry of Gold Fluoride Complexes","authors":"W. Wolf, F. Toste","doi":"10.1002/9780470682531.PAT0819","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0819","url":null,"abstract":"The gold-fluorine bond represents a rare class of chemical bond, with only a handful of notable examples having been prepared and characterized. The extreme reactivity of the homoleptic gold fluorides AuF, AuF3, and AuF5 makes these compounds difficult to prepare and has limited their applications beyond fundamental study. However, the inherent reactivity of the gold fluoride bond can be harnessed by using ancillary ligands to support the metal center. Heteroleptic gold fluorides containing both Au(I) or Au(III) centers have been prepared and have found applications in catalysis, where the gold-fluoride bond is implicated as a key reactive moiety. The present review summarizes the preparation of both homo- and heteroleptic gold fluoride complexes and the development of catalytic transformations involving gold-fluoride bonds. \u0000 \u0000 \u0000Keywords: \u0000 \u0000catalysis; \u0000gold; \u0000fluorine; \u0000organometallics; \u0000oxidation","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"10 1","pages":"1-18"},"PeriodicalIF":0.0,"publicationDate":"2014-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73058145","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Sulfoxylic and Thiosulfurous Acids and their Dialkoxy Derivatives","authors":"S. Makarov, A. Makarova, R. Silaghi-Dumitrescu","doi":"10.1002/9780470682531.PAT0829","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0829","url":null,"abstract":"Being potent reductants, sulfoxylic acid S(OH)2 and its salts (sulfoxylates) are intermediates in many reactions of important industrial chemicals, such as sodium hydroxymethanesulfinate (rongalite) and thiourea dioxide. Sulfoxylates contain the -O-S-O- moiety, which is isoelectronic to trioxides, -O-O-O-. However, the apparent structural and valence electron count similarity may be contrasted to significant differences in reactivity. \u0000 \u0000 \u0000 \u0000Thiosulfurous acid H2S2O2 is a primary product of reaction between hydrogen sulfide and sulfur dioxide. Despite the central role of the S-S bond in organic, inorganic and biological chemistry, thiosulfurous acid remains one of the least studied sulfur acids together with its one sulfur counterpart–sulfoxylic acid. Here we present the first special review describing the structure, stability and reactivity of these acids and their anions. \u0000 \u0000 \u0000 \u0000Organic derivatives of sulfoxylic and thiosulfurous acids are much more studied than the acids themselves. In this review, organic derivatives of sulfoxylic and thiosulfurous acids (dialkoxy sulfoxylates (R-O-S-O-R) and dialkoxy disulfides (R-O-S-S-O-R), which are isoelectronic to organic trioxides and tetroxides), as well as organic trisulfanes R-S-S-S-R and tetrasulfanes R-S-S-S-S-R, respectively, are also briefly discussed. \u0000 \u0000 \u0000Keywords: \u0000 \u0000dialkoxy disulfides; \u0000dialkoxy sulfoxylates; \u0000reactivity; \u0000structure; \u0000sulfoxylic acid; \u0000thiosulfurous acid","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"21 20","pages":"1-42"},"PeriodicalIF":0.0,"publicationDate":"2014-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91446854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Gold‐Catalyzed Migrations and Ring Expansions","authors":"E. Merino, L. Fernández, C. Nevado","doi":"10.1002/9780470682531.PAT0811","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0811","url":null,"abstract":"Gold complexes have been used to π-activate alkynes, alkenes, and related moieties due to their strong affinity for these carbon systems. In this chapter we have summarized first, the most representative examples of gold-catalyzed migrations occurring in propargylic systems and classified them according to the nature of the migrating group. In the second part, we have compiled the most relevant gold-catalyzed ring expansions according to ring size. The current mechanistic understanding of these transformations is also presented. \u0000 \u0000 \u0000Keywords: \u0000 \u0000π-activation; \u0000gold catalysis; \u0000migrations; \u0000propargyl esters; \u0000ring expansions","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"82 1","pages":"1-72"},"PeriodicalIF":0.0,"publicationDate":"2014-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72711885","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synthesis and Reactivity of Gold–Olefin Complexes","authors":"C. Dash, H. V. Rasika Dias","doi":"10.1002/9780470682531.PAT0816","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0816","url":null,"abstract":"Gold catalysts have been used at an increasing frequency to facilitate a wide variety of organic transformations in synthetic organic chemistry. Among these, the functionalization of CC multiple bonds (alkenes or alkynes) in the presence of gold catalysts are some of the most important strategies utilized for the construction of CC, CO and CN bonds. A majority of these reactions are believed to proceed via gold-bound alkene (olefin) or alkyne intermediates. This chapter highlights some of the recent developments on the syntheses of gold-olefin complexes and their spectroscopic data and structural features. In addition, gold mediated inter- and intra-molecular nucleophilic addition reactions of nitrogen, oxygen or carbon nucleophiles to olefins are discussed. Reaction mechanisms of these nucleophilic addition reactions, in which goldolefin adducts have been proposed as intermediates, are also presented. \u0000 \u0000 \u0000Keywords: \u0000 \u0000alkenes; \u0000gold; \u0000homogeneous catalysis; \u0000π-complexes; \u0000nucleophilic additions; \u0000reaction mechanisms; \u0000transition metals","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"79 1","pages":"1-40"},"PeriodicalIF":0.0,"publicationDate":"2014-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75336327","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Gold-Catalyzed Addition of HX to Alkynes","authors":"E. Genin, V. Michelet","doi":"10.1002/9780470682531.PAT0814","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0814","url":null,"abstract":"Among the myriad of organic transformations that have been developed in the area of gold catalysis, the addition of HX to alkynes has been a field of intense investigation. This chapter presents the main and recent contributions in the field of gold-catalyzed nucleophilic addition of HX to alkynes. The presentation includes the addition of O-nucleophiles (including water, alcohols and carboxylic acids), of N-nucleophiles and other heteroatom nucleophiles (including thiols and halogens) to alkynes. The historical background for inter- and intramolecular additions, the domino processes and the applications to natural products synthesis are highlighted. \u0000 \u0000 \u0000Keywords: \u0000 \u0000alcohol; \u0000alkyne; \u0000amide; \u0000amine; \u0000carboxylic acid; \u0000gold; \u0000heterocycle; \u0000nucleophilic addition; \u0000thiol","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"35 1","pages":"1-60"},"PeriodicalIF":0.0,"publicationDate":"2014-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78705102","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Catalysis of Organic Transformations by Gold Nanoparticles Supported on Metal Oxides","authors":"M. Stratakis, H. García","doi":"10.1002/9780470682531.PAT0817","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0817","url":null,"abstract":"Supported gold nanoparticles on metal oxides surfaces are powerful catalysts applicable to a variety of organic transformations. Following the first observation that they activate molecular oxygen towards oxidation of CO or organic compounds (e.g. alcohols) under mild conditions, it was uncovered during the past decade that Au nanoparticles activate alkynes, silanes, dihydrogen, exhibit oxophilic activity, catalyze CC bond forming cross-coupling reactions and transfer hydrogenation processes, thus mimicking the catalytic activity of Pd, Pt, and other late transition metals. \u0000 \u0000 \u0000Keywords: \u0000 \u0000catalysis; \u0000cross-coupling reactions; \u0000gold nanoparticles; \u0000isomerization; \u0000oxidation; \u0000reduction","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"9 4 1","pages":"1-58"},"PeriodicalIF":0.0,"publicationDate":"2014-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78309045","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Organic Tetroxides and Mechanism of Peroxy Radical Recombination","authors":"S. Khursan","doi":"10.1002/9780470682531.PAT0827","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0827","url":null,"abstract":"The chemical properties of organic tetroxides, that is, compounds of a general formula ROOOOR (R = H or organic radical) are discussed. The following tetroxides are considered: hydrogen tetroxide HOOOOH, dialkyl tetroxides ROOOOR, hydrotetroxides ROOOOH, and five-membered cyclic tetroxides—tetroxolanes. Hydrogen tetroxide is formed via self-reaction of HOO· radicals on singlet PES; hydroperoxy radical interaction plays an important role in the chemistry of atmosphere. The formation and subsequent decay of tetroxides are discussed in detail. Similar self-reaction of alkylperoxy radicals leads to organic tetroxides. Its irreversible transformation occurs in two directions depending on the tetroxide structure: the facile homolysis of ROOOOR bond or the induced by αCH bond radical decomposition of tetroxide into hydroperoxy, alkoxy radicals, and carbonyl compound. The latter interaction is the key step in the new mechanism of peroxy radical recombination suggested on the base of extensive analysis of available literature. Hydrotetroxides show properties similar to both HOOOOH and dialkyl tetroxides. A possibility of tetroxolane generation in the reaction of ozone with carbonyl compounds is discussed. \u0000 \u0000 \u0000Keywords: \u0000 \u0000free radicals; \u0000organic tetroxides; \u0000oxidation; \u0000ozone; \u0000reaction mechanism; \u0000singlet oxygen; \u0000tetroxolanes; \u0000thermal decomposition","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"19 1 1","pages":"1-34"},"PeriodicalIF":0.0,"publicationDate":"2014-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84830174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
P. Mascio, S. Miyamoto, M. Medeiros, G. Martinez, J. Cadet
{"title":"[18O]‐Peroxides: Synthesis and Biological Applications","authors":"P. Mascio, S. Miyamoto, M. Medeiros, G. Martinez, J. Cadet","doi":"10.1002/9780470682531.PAT0868","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0868","url":null,"abstract":"The peroxidation reactions of the main cellular targets including nucleic acids, proteins and unsaturated lipids have received major attention during the last two decades. This was particularly the case for the hydroperoxides generated by 1O2, one of the main reactive oxygen species that usually oxidizes biomolecules in a more specific way than either •OH or one-electron oxidants. Most of the endoperoxides and hydroperoxides produced by 1O2 have been shown to be unstable and therefore their identification is often difficult. The use of [18O]-labeled 1O2 released from thermolabile endoperoxides in association with HPLC-ESI-MS/MS analysis provides a highly suitable way to gain relevant mechanistic insights into the formation and the decomposition pathways of initially generated peroxidic compounds. The possibility of cell penetration afforded by suitable naphthalene endoperoxides has also been exploited for investigating the reaction of 1O2 with DNA for accrediting the mechanism of oxidation of guanine in the nucleus and providing an elegant approach for assessing the validity of DNA isolation methods used in the measurement of 8-oxo-7,8-dihydroguanine, an ubiquitous oxidation product. Further developments are expected both in mechanistic studies and applications in cells using [18O]-labeled 1O2 generators. Keywords: [18O]-Peroxides; hydroperoxides; [18O]-labeled singlet molecular oxygen; mass spectrometry; [18O]-labeled molecular oxygen; naphthalene endoperoxides; DNA; protein; cardiolipin; lipid","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"76 1","pages":"1-36"},"PeriodicalIF":0.0,"publicationDate":"2014-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86926588","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Coordination Chemistry of Metal Phenolates—General Aspects","authors":"L. Doerrer","doi":"10.1002/9780470682531.PAT0604","DOIUrl":"https://doi.org/10.1002/9780470682531.PAT0604","url":null,"abstract":"An overview of metal phenolate chemistry is given that highlights the structural and functional diversity of contemporary chemistry between metals from all parts of the periodic table and aryloxide ligands. After a brief overview of synthetic methods, the review is organized using structural characterization, but is not exclusive of non-structurally characterized species. Monodentate and polydentate ligands are described and organized by the type and number of donor atoms. Within each section, the chemistry is further subdivided by the periodic table s-, p-, d-, and f-blocks. Extensive references to the literature are provided for the interested reader. \u0000 \u0000 \u0000Keywords: \u0000 \u0000metal; \u0000transition metal; \u0000phenolate; \u0000aryloxide; \u0000complex; \u0000polymerization; \u0000ring-opening; \u0000biomimetic; \u0000SMM; \u0000SOC","PeriodicalId":20036,"journal":{"name":"Patai's Chemistry of Functional Groups","volume":"41 1","pages":"1-90"},"PeriodicalIF":0.0,"publicationDate":"2014-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78889149","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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