102410-96-8Relevant academic research and scientific papers
Symmetric Bridgehead-to-Bridgehead Coupling of Bicyclo[1.1.1]pentanes and [n]Staffanes
Mazal, Ctibor,Paraskos, Alex J.,Michl, Josef
, p. 2116 - 2119 (1998)
Symmetrical bridgehead-to-bridgehead coupling of bicyclo[1.1.1] pentane cages has been effected in 48-70% yields by the cuprate oxidation method.
A Facile, Palladium-Catalyzed Synthesis of 1,1'Bi(cyclo[1.1.1]pentanes)
Rehm, J. D. Daniel,Ziemer, Burkhard,Szeimies, Guenter
, p. 1049 - 1052 (2001)
Symmetrically 3,3'-disubstituted 1,1'-bi(bicyclo[1.1.1]pentanes) were synthesized in a four-step procedure, using commercially available starting materials, in fair overall yields (51-60%).In this synthesis the final step is an unexpected bridgehead-t-bridgehead homocoupling of bicyclo[1.1.1]pent-1-ylmagnesium halide catalyzed by palladium(II). Only 1.1 mol percent of bis(acetonitrile)palladium(II) chloride and two equivalents of bromoethane were necessary to accomplish this reaction. the bromoethane is essential to convert Pd0 into PdII. The X-ray structure of the C1-C3-distance of 1.907 Angstroem in the bicyclo[1.1.1]pentyl subunit.
1,3-bicyclo[1.1.1]pentanediyl: The shortest rigid linear connector of phenylated photochromic units and a 1,5-dimethoxy-9,10-di(phenylethynyl) anthracene fluorophore
De Meijere, Armin,Ligang, Zhao,Belov, Vladimir N.,Bossi, Mariano,Noltemeyer, Matthias,Hell, Stefan W.
, p. 2503 - 2516 (2008/04/01)
An excess of bis-1,3-(4-iodophenyl)bicyclo[1.1.1]pentane, prepared in 63% yield by iodination of 1.3-diphenylbicyclo[1.1.1]pentane, was selectively mono-coupled with 9-ethynyl-1,5-dimethoxy-10-phenylethynylanthracene (26), and subsequently with the zinc derivatives of 1-(2-methyl/methoxy-4-methyl-5- phenylthiophen-3-yl)-2-(2-methyl/methoxy-4-methylthiophen-3-yl) perfluorocyclopentenes (38-H-41-H). Regioselective synthesis of the 2-unsubslituted thiophenes 38-H-41-H required intermediate prepara tion of 2-trimethylsilyl-3,5-dimethyl-4-bromothiophene (37) or 2-trimethylsilyl-5- methoxy-3-methyl-4-bromothiophene (40). Protection of the α-position of the thiophene ring with a 2-trimethylsilyl group blocks the rearrangement of the 4-lithio derivatives into the corresponding 2-lithiated thiophenes. With the bicyclo[1.1.1]pentane frag ment linking the photochromic units 1-3 and 1,5-dimethoxy-9,10-di(phenylethynyl)anthracene as a fluorescent part, quantitative resonance energy transfer between the excited state of the fluorophore (donor) and the closed form of the photochromic units 1-3 (acceptors) was observed. The closed forms of the methoxy-substituted photochromic units 2 and 3 are less resistant to UV light (313 nm) than the closed form of 1.
Nickel- and palladium-catalyzed cross-coupling reactions at the bridgehead of bicyclo[1.1.1]pentane derivatives - A convenient access to liquid crystalline compounds containing bicyclo[1.1.1]pentane moieties
Messner, Matthias,Kozhushkov, Sergei I.,De Meijere, Armin
, p. 1137 - 1155 (2007/10/03)
Radical addition reactions of organyl iodides 7a-s onto [1.1.1]propellane (2) followed by halogen-lithium exchange and transmetallation with zinc chloride, as well as additions of Grignard reagents to 2, have furnished a variety of 3-substituted bicyclo[1.1.1]pentyl-1-magnesium (14) and -zinc (19) derivatives. The latter have been coupled with various alkenyl, aryl, and biaryl halides and triflates under NiCl2dppe, Pd(PPh3)4, or PdCl2(dppf) catalysis to give a number of 1,3-disubstituted bicyclo[1.1.1]pentyl derivatives 17, 20, and 23, several of which exhibit liquid crystalline properties, in moderate to very good yields. The coupling products 20ca, 23ab, 23ae, 23ff, and 23fg have been further transformed to yield bicyclo[1.1.1]pentyl derivatives 32, 24ab, 24ae, 27ff, and 27fg, respectively, bearing alkynyl, cyano, and/or alkenyl groups.
Replecement of the carboxylic acid function with fluorine
Patrick, Timothy B.,Johri, Kamalesh K.,White, David H.,Bertrand, William S.,Mokhtar, Rodziah,et al.
, p. 138 - 141 (2007/10/02)
Replacement of a carbonyl function by fluorine, fluorodecarboxylation, is a new process that can be accomplished by the reaction of alkanoic acids with xenon difluoride.Primary, tertiary, and benzylic acids perform best in the reaction, which is conducted at room temperature in methylene chloride or chloroform solution.A reaction mechanism is proposed in which the acid is initially converted to a fluoroxenon ester, RCO2XeF.The esters of the primary and secondary acids react by nucleophilic displacement by fluoride, as evidenced by incorporation of 18F- and no reactions common to free radicals or carbocations.The esters of the tertiary and benzylic acids react by converting to free radicals that can be further oxidized to carbocations.Thus incorporation of 18F- and racemization are observed with α-methoxy-α-trifluoromethylphenylacetic acid.Hydroxyl and amino functions inhibit the reaction.Aromatic and vinylic acids do not react.
