14651-42-4Relevant articles and documents
Preparation and Properties of 1-Adamantylmethyl and Adamantyl Complexes of Transition Metals
Bochmann, Manfred,Wilkinson, Geoffrey,Young, Brent G.
, p. 1879 - 1887 (1980)
The syntheses and characteristic properties of a variety of 1-adamantylmethyl (R = 1-adme) compounds of transition metals are described.These include peralkyls, MRn (M = Ti,V,Cr,Mn, or Zr); mixed complexes, MRnXm (X = OtBu or Cl, M = V, Nb or Ta); ?-acid complexes, MR2L2 (L = P- or N-donor) including the first example of a thermodinamically favoured trans-dialkylplatinum(II) derivative.Additionally, the preparations of bis(1-adamantyl)- and bis(2-adamantyl)-magnesium are reported, as well as successful and inconclusive attempts to produce Cr(ad)4 (ad = 1- or 2-adamantyl).
Transmembrane anion transport mediated by adamantyl-functionalised imidazolium salts
Gravel, Julien,Schmitzer, Andreea R.
, p. 364 - 371 (2015)
We present the design, synthesis and transmembrane anion transport properties of a new class of mobile organic transporters, possessing a central imidazolium cation and two external adamantyl units. We demonstrate herein that the imidazolium cation can be incorporated in the structure of active mobile anion transporters. Depending on the nature of the counter-anion of the salt, as well as the extravesicular anions, different anion selectivities were obtained. We show the importance of the H2 proton of the imidazolium cation in order to obtain a higher binding constant of the chloride anion. Furthermore, we demonstrate the importance of the flexibility of the spacers between the adamantyl groups and the imidazolium cation in the transport process.
Three-Component, Interrupted Radical Heck/Allylic Substitution Cascade Involving Unactivated Alkyl Bromides
Bellotti, Peter,Glorius, Frank,Heidrich, Bastian,Huang, Huan-Ming,Pflüger, Philipp M.,Schwarz, J. Luca
supporting information, p. 10173 - 10183 (2020/06/27)
Developing efficient and selective strategies to approach complex architectures containing (multi)stereogenic centers has been a long-standing synthetic challenge in both academia and industry. Catalytic cascade reactions represent a powerful means of rapidly leveraging molecular complexity from simple feedstocks. Unfortunately, carrying out cascade Heck-type reactions involving unactivated (tertiary) alkyl halides remains an unmet challenge owing to unavoidable β-hydride elimination. Herein, we show that a modular, practical, and general palladium-catalyzed, radical three-component coupling can indeed overcome the aforementioned limitations through an interrupted Heck/allylic substitution sequence mediated by visible light. Selective 1,4-difunctionalization of unactivated 1,3-dienes, such as butadiene, has been achieved by employing different commercially available nitrogen-, oxygen-, sulfur-, or carbon-based nucleophiles and unactivated alkyl bromides (>130 examples, mostly >95:5 E/Z, >20:1 rr). Sequential C(sp3)-C(sp3) and C-X (N, O, S) bonds have been constructed efficiently with a broad scope and high functional group tolerance. The flexibility and versatility of the strategy have been illustrated in a gram-scale reaction and streamlined syntheses of complex ether, sulfone, and tertiary amine products, some of which would be difficult to access via currently established methods.
PROCESS FOR THE PREPARATION OF ORGANIC BROMIDES
-
Paragraph 00169; 00171; 00200, (2017/07/28)
The present invention provides a process for the preparation of organic bromides, by a radical bromodecarboxylation of carboxylic acids with a bromoisocyanurate.
Synthesis and characterization of sterically enlarged hoveyda-type olefin metathesis catalysts
Shahane, Saurabh,Toupet, Loic,Fischmeister, Cedric,Bruneau, Christian
supporting information, p. 54 - 60 (2013/03/13)
A series of four ruthenium-based olefin metathesis catalysts has been prepared. These new complexes were designed with nanofiltration in organic media in mind; steric enlargement and functionalisation by means of polar ethylene glycol chains were incorporated. New complexes based on the stable 2nd generation Hoveyda-type architecture and featuring substitution either on the NHC backbone or on the N-aryl substituent of the NHC have been prepared and fully characterized. The application of these complexes in a series of olefin metathesis transformations revealed that these modified catalysts retained activity on par with the parent Hoveyda catalyst thus validating the disclosed ligand design.
Covalently supported porphyrins as ligands for the preparation of heme a3/CuB binuclear active site analogues of heme-copper terminal oxidases and metallation under mild conditions
Baeg, Jin-Ook
, p. 571 - 572 (2007/10/03)
New covalently supported binucleating porphyrins have been prepared as potential structural and/or functional ligands for the iron-copper (heme a3/CuB) active sites of heme-copper oxidases, and the introduction of iron and copper into one porphyrin under mild reaction conditions has been developed.
REACTION OF ALCOHOLS WITH BROMINE
Baklan, V. F.,Khil'chevskii, A. N.,D'yakovskaya, V. M.,Sologub, L. S.,Kukhar, V. P.
, p. 454 - 456 (2007/10/02)
Framework hydrocarbons react with bromine in water to form tertiary alcohols.In the absence of moisture the various alcohols react with bromine by a nucleophilic substitution mechanism, forming alkyl bromides.
An EPR Study of 1-Adamantylmethyl Radicals
Davies, Alwyn G.,Neville, Anthony G.
, p. 2021 - 2024 (2007/10/02)
The 1-adamantylmethyl, di(1-adamantyl)methyl, and tri(1-adamantyl)methyl radicals have been prepared by photolysis of hexabutylditin in the presence of the corresponding bromide, the 1-adamantylhydroxymethyl radical by photolysis of di-tert-butyl peroxide in the presence of 1-adamantylmethanol, and the di-1-adamantylketyl radical anion by photolysis of di-1-adamantyl ketone in the presence of sodium-potassium alloy.The EPR 1H and 13C hyperfine coupling constants which are observed in these radicals and in the tetra-1-adamantylcyclobutadiene radical cation are discussed in terms of the structures of the radicals.The di-1-adamantylmethyl radical decays in cyclopentane at 310 K and in toluene at 180-240 K by clean pseudo first-order kinetics.The reaction is much faster in the latter solvent, implying that it involves abstraction of benzylic hydrogen.At 190 K in pentane, the decay shows second-order kinetics.The decay of the tri-1-adamantylmethyl radical shows more complicated behaviour.
Competitive and Regiospecific Bridgehead Substitution in Electrophilic Oxidation Reactions of Homoadamantane
Israel, Robert J.,Murray, Roger K.
, p. 4701 - 4705 (2007/10/02)
Oxidation of homoadamantane with chromic acid, lead tetraacetate, p-nitroperbenzoic acid, or bromine occurs by competitive attack at the C-3 (major) and C-1 (minor) bridgehead positions.In striking contrast, dry ozonation of homoadamantane adsorbed on silica gel leads to regiospecific substitution at the chemically equivalent C-3 and C-6 bridgehead positions.A consequence of this observation is that some 1,3- and 3,6-disubstituted homoadamantanes can be prepared by dry ozonation of suitably substituted homoadamantane derivatives.
The Barbier Synthesis: A One-Step Grignard Reaction?
Molle, Gerard,Bauer, Pierre
, p. 3481 - 3487 (2007/10/02)
Counter to generally accepted theory, it is demonstrated that the Byrbier synthesis does not necessarily involve the in situ formation of an organometallic compound.In certain cases, there is a radical pathway in which the anion radical (R.-X-) resulting from the attack by a halogenated derivative on lithium is directly trapped by the ketone or by the ketyl radical on the metal surface befor the organometallic compound forms.This pathway can be unique, as when 1-bromoadamantane condenses with adamantanone or hexamethylacetone.However, by extension of the Barbier synthesis to other "cage-structure" compounds homologous to adamantane, it is seen that the radical pathway can compete with the organometallic pathway and that this competition is principally determined by the stability of the cage radicals generated at the metal-solution interface.An optimum yield can be attained in this type of synthesis by choosing the Grignard reaction or the Barbier reaction, depending on the nature of the halogenated cage derivatives in use.
