100-86-7Relevant articles and documents
Reactivity of a Palladacyclic Complex: A Monodentate Carbonate Complex and the Remarkable Selectivity and Mechanism of a Neophyl Rearrangement
Behnia, Ava,Fard, Mahmood A.,Blacquiere, Johanna M.,Puddephatt, Richard J.
, p. 4759 - 4769 (2017)
The ligand N(CH2-2-C5H4N)2(CH2CH2CH2OH), L1, reacted with [Pd(CH2CMe2C6H4)(COD)] to give a new fluxional cycloneophyl organopalladium complex [Pd(CH2CMe2C6H4)(κ2-L1)], 1, which on attempted recrystallization from THF gave the monodentate carbonate complex [Pd(CO3)(κ3-L1)], 2. Complex 2 was prepared in designed syntheses by reaction of [PdCl(κ3-L1)]+ with silver carbonate or by reaction of [Pd(OH)(κ3-L1)]+ with CO2. Complex 1 reacted with aqueous CO2 to give the cationic neophylpalladium complex [Pd(CH2CMe2C6H5)(κ3-L1)]+(HCO3)-, 6. Complex 6 reacts with hydrogen peroxide to give complex 2 with release of a mixture of organic products, the major one being 2-phenyl-2-butanol, PB. The formation of PB involves a neophyl rearrangement with the unprecedented preference for methyl over phenyl migration. A mechanistic basis for this unexpected reaction is proposed, involving β-carbon elimination at a palladium(IV) center.
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Tiffeneau,Delange
, p. 575 (1903)
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Catalytic Replacement of Unactivated Alkane Carbon-Hydrogen Bonds with Carbon-X Bonds (X = Nitrogen, Oxygen, Chlorine, Bromine, or Iodine). Coupling of Intermolecular Hydrocarbon Activation by MnIIITPPX Complexes with Phase-Transfer Catalysis
Hill, Craig L.,Smegal, John A.,Henly, Timothy J.
, p. 3277 - 3281 (1983)
A simple system has been devised to facilitate the first processes for the catalytic replacement of unactivated alkane C-H bonds with C-X bonds, X = nitrogen and iodine.The system also enables alkane C-H bonds to be replaced by C-X bonds, X = chlorine, bromine, and oxygen.The system is composed of two liquid phases and the oxidant iodosylbenzene (iodosobenzene).The alkane substrate, the MnIIITPPX catalyst, and the organic solvent (dichloromethane, chlorobenzene, or other aromatic hydrocarbon) constitute one phase, a saturated aqueous solution of the sodium salt of the anion to be incorporated into the alkane, NaX, X = N3(1-), NCO(1-), I(1-), Br(1-), or Cl(1-), constitutes the second phase, and the sparingly soluble oxidant iodosylbenzene constitutes a third phase.When the two liquid phases and the oxidant iodosylbenzene are stirred under an inert atmosphere, both RX and ROH products are produced catalytically based on MnTPP and in reasonable yield based on iodosylbenzene.The MnTPP moiety functions as a catalyst for C-H bond cleavage and for phase transfer of X(1-) from the aqueous phase to the organic phase where the functionalization chemistry takes place.The oxidant hypochlorite can be used in place of, but is less effective than, iodosylbenzene, and the oxidants hydrogen peroxide, periodate, and persulfate are ineffective.Product distributions obtained from the oxidation of cyclohexane, isobutane, 2,3-dimethylbutane, and tert-butylbenzene are most consistent with a product-determining step that involves transfer of X from manganese to a free alkyl radical intermediate.
Use of Sacrificial Anodes in Electrochemical Functionalization of Organic Halides
Chaussard, Jacques,Folest, Jean-Claude,Nedelec, Jean-Yves,Perichon, Jacques,Sibille, Soline,Troupel, Michel
, p. 369 - 381 (1990)
This article reviews the new possibilities in organic synthesis offered by the electroreduction of organic halides in the presence of various electrophiles using sacrificial metallic anodes.
Model dialkyl peroxides of the fenton mechanistic probe 2-methyl-1-phenyl-2-propyl hydroperoxide (MPPH): Kinetic probes for dissociative electron transfer
Magri, David C.,Workentin, Mark S.
, p. 3418 - 3429 (2003)
Two dialkyl peroxides, devised as kinetic probes for the heterogeneous electron transfer (ET), are studied using heterogeneous and homogeneous electrochemical techniques. The peroxides react by concerted dissociative ET reduction of the O-O bond. Under heterogeneous conditions, the only products isolated are the corresponding alcohols from a two-electron reduction as has been observed with other dialkyl peroxides studied to date. However, under homogeneous conditions, a generated alkoxyl radical undergoes a rapid β-scission fragmentation in competition with the second ET resulting in formation of acetone and a benzyl radical. With knowledge of the rate constant for fragmentation and accounting for the diffuse double layer at the electrode interface, the heterogeneous ET rate constant to the alkoxyl radicals is estimated to be 1500 cm s-1. The heterogeneous and homogeneous ET kinetics of the O-O bond cleavage have also been measured and examined as a function of the driving force for ET, ΔGET, using dissociative electron transfer theory. From both sets of kinetics, besides the evaluation of thermochemical parameters, it is demonstrated that the heterogeneous and homogeneous reduction of the O-O bond appears to be non-adiabatic.
Abenhaim,Namy
, p. 3011,3012 (1972)
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Frank,Foster
, p. 1019 (1954)
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McHatton, Ron C.,Espenson, James H.,Bakac, Andreja
, p. 3531 - 3533 (1982)
Highly powerful and practical acylation of alcohols with acid anhydride catalyzed by Bi(OTf)3
Orita,Tanahashi,Kakuda,Otera
, p. 8926 - 8934 (2001)
Bi(OTf)3-catalyzed acylation of alcohols with acid anhydride was evaluated in comparison with other acylation methods. The Bi(OTf)3/acid anhydride protocol was so powerful that sterically demanding or tertiary alcohols could be acylated smoothly. Less reactive acylation reagents such as benzoic and pivalic anhydride are also activated by this catalysis. In these cases, a new technology was developed in order to overcome difficulty in separation of the acylated product from the remaining acylating reagent: methanolysis of the unreacted anhydride into easily separable methyl ester realized quite easy separation of the desired acylation product. The Bi(OTf)3/acid anhydride protocol was applicable to a wide spectrum of alcohols bearing various functionalities. Acid-labile THP- or TBS-protected alcohol, furfuryl alcohol, and geraniol could be acylated as well as base-labile alcohols. Even acylation of functionalized tertiary alcohols was effected at room temperature.
UN NOVEAU SYNTHON ORGANOSILICIE: LE BENZYLTRIMETHYLSILANE
Bennetau, Bernard,Dunogues, Jacques
, p. 4217 - 4218 (1983)
In the presence of tetrabutylammonium fluoride (TBAF) as the catalyst, benzyltrimethylsilane adds to aldehydes and ketones to afford, upon hydrolysis, the corresponding alcohols.The use of PhCH2SiMe3 as a general benzylation reagent is here reported for the first time.
Generation of Anionic Intermediates by Intramolecular Nucleophilic Attack at Silicon
Hudrlik, Paul F.,Abdallah, Yousef M.,Hudrlik, Anne M.
, p. 6747 - 6750 (1992)
Benzyl and allyl anion equivalents can be generated from benzyl- and allylsilanes by intramolecular alkoxide attack.
Controlled stepwise release of fragrance alcohols from dendrimer-based 2-carbamoylbenzoates by neighbouring group participation
Frerot, Eric,Herbal, Karim,Herrmann, Andreas
, p. 967 - 971 (2003)
2-Carbamoylbenzoates which are chemically bound to the surface of dendrimers were found to release tertiary fragrance alcohols by neighbouring group assisted alkaline hydrolysis under mild reaction conditions. Owing to the excellent separation of the intermediate reaction products by analytical HPLC, the kinetic rate constants of the first two consecutive reaction steps of fragrance release could be determined for a series of modified dendrimers with increasing size. Because of the intramolecular neighbouring group effect, the kinetic rate constants were found to be independent of the dendrimer generation and are not influenced by steric effects on the surface of the macromolecules. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).
Samarium-mediated Barbier reaction of carbonyl compounds
Basu, Manas K.,Banik, Bimal K.
, p. 187 - 189 (2001)
Samarium metal in the presence of catalytic amounts of iodine was found to be effective for the Barbier reaction of carbonyl compounds.
REACTIVITE DE LA LIAISON δ ACTINIDE-CARBONE : LE TRIS(BISTRIMETHYLSILYLAMIDO)METHYLURANIUM, UN AGENT METHYLANT NUCLEOPHILE A HAUTE SELECTIVITE
Dormond, A.,Aaliti, A.,Moise,, C.
, p. 1497 - 1498 (1986)
The title compound 1 reacts with carbonyl derivatives as a very highly selective nucleophilic methylating reagent.
Tuning the Diiron Core Geometry in Carboxylate-Bridged Macrocyclic Model Complexes Affects Their Redox Properties and Supports Oxidation Chemistry
Wang, Fang,Becker, Sabine,Minier, Mikael A.,Loas, Andrei,Jackson, Megan N.,Lippard, Stephen J.
, p. 11050 - 11058 (2017)
We introduce a novel platform to mimic the coordination environment of carboxylate-bridged diiron proteins by tethering a small, dangling internal carboxylate, (CH2)nCOOH, to phenol-imine macrocyclic ligands (H3PIMICn). In the presence of an external bulky carboxylic acid (RCO2H), the ligands react with [Fe2(Mes)4] (Mes = 2,4,6-trimethylphenyl) to afford dinuclear [Fe2(PIMICn)(RCO2)(MeCN)] (n = 4-6) complexes. X-ray diffraction studies revealed structural similarities between these complexes and the reduced diiron active sites of proteins such as Class I ribonucleotide reductase (RNR) R2 and soluble methane monooxygenase hydroxylase. The number of CH2 units of the internal carboxylate arm controls the diiron core geometry, affecting in turn the anodic peak potential of the complexes. As functional synthetic models, these complexes facilitate the oxidation of C-H bonds in the presence of peroxides and oxo transfer from O2 to an internal phosphine moiety.
Sulfonium ion-promoted traceless Schmidt reaction of alkyl azides
Ardiansah, Bayu,Kakiuchi, Kiyomi,Morimoto, Tsumoru,Tanimoto, Hiroki,Tomohiro, Takenori
supporting information, p. 8738 - 8741 (2021/09/08)
Schmidt reaction by sulfonium ions is described. General primary, secondary, and tertiary alkyl azides were converted to the corresponding carbonyl or imine compounds without any trace of the activators. This bond scission reaction through 1,2-migration of C-H and C-C bonds was accessible to the one-pot substitution reaction.
An Enantioconvergent Benzylic Hydroxylation Using a Chiral Aryl Iodide in a Dual Activation Mode
Abazid, Ayham H.,Clamor, Nils,Nachtsheim, Boris J.
, p. 8042 - 8048 (2020/09/21)
The application of a triazole-substituted chiral iodoarene in a direct enantioselective hydroxylation of alkyl arenes is reported. This method allows the rapid synthesis of chiral benzyl alcohols in high yields and stereocontrol, despite its nontemplated nature. In a cascade activation consisting of an initial irradiation-induced radical C-H-bromination and a consecutive enantioconvergent hydroxylation, the iodoarene catalyst has a dual role. It initiates the radical bromination in its oxidized state through an in-situ-formed bromoiodane and in the second, Cu-catalyzed step, it acts as a chiral ligand. This work demonstrates the ability of a chiral aryl iodide catalyst acting both as an oxidant and as a chiral ligand in a highly enantioselective C-H-activating transformation. Furthermore, this concept presents an enantioconvergent hydroxylation with high selectivity using a synthetic catalyst.
