2762-93-8Relevant academic research and scientific papers
An Electroreductive Approach to Radical Silylation via the Activation of Strong Si-Cl Bond
Lu, Lingxiang,Siu, Juno C.,Lai, Yihuan,Lin, Song
supporting information, p. 21272 - 21278 (2020/12/21)
The construction of C(sp3)-Si bonds is important in synthetic, medicinal, and materials chemistry. In this context, reactions mediated by silyl radicals have become increasingly attractive but methods for accessing these intermediates remain limited. We present a new strategy for silyl radical generation via electroreduction of readily available chlorosilanes. At highly biased potentials, electrochemistry grants access to silyl radicals through energetically uphill reductive cleavage of strong Si-Cl bonds. This strategy proved to be general in various alkene silylation reactions including disilylation, hydrosilylation, and allylic silylation under simple and transition-metal-free conditions.
DTBB-Catalysed dilithiation of styrene and its methyl-derivatives: Introduction of two electrophilic reagents
Yus, Miguel,Martínez, Pedro,Guijarro, David
, p. 10119 - 10124 (2007/10/03)
The reaction of styrene and some methyl-substituted styrenes 1 with lithium and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB) in the presence of several electrophiles [Me3SiCl, Me2CO, Et2CO, (CH2)5CO, Pr2CO], in THF, at temperatures ranging from -78 to 0°C, gave, after hydrolysis, products 2 resulting from addition of lithium to the olefinic double bond and successive trapping with the electrophilic reagent. When a carbonyl compound was used as electrophile, mixtures of the monoaddition-reduction compounds 3 and 4 were obtained as by-products, which could be easily separated from the diaddition products 2.
Electrochemically Promoted Cyclocoupling of 1,3-Dienes or Styrenes with Aliphatic Carboxylic Esters
Shono, Tatsuya,Ishifune, Manabu,Kinugasa, Hiroshi,Kashimura, Shigenori
, p. 5561 - 5563 (2007/10/02)
The cathodic cyclocoupling of 1,3-dienes 1 with aliphatic esters 2 is promoted by a magnesium electrode and yields homologs of 3-cyclopentenol.Under similar reaction conditions, the coupling of styrenes with 2 affords 2-phenylcyclopropanol derivatives, an
Carbanion Rearrangements by Intramolecular 1,ω Proton Shifts, III. The Reaction of 2-, 3-, 4-, and 5-Phenylalkyllithium Compounds
Maercker, Adalbert,Passlack, Michael
, p. 540 - 577 (2007/10/02)
Upon addition of THF to a solution of 4-phenylbutyllithium (2) in diethyl ether a rapid intramolecular 1,4 proton shift takes place with the formation of 1-phenylbutyllithium (5).Similarly, although somewhat more slowly, 5-phenylpentyllithium (82) rearranges to 1-phenylpentyllithium (83) via 1,5 proton transfer.The corresponding rearrangements by 1,2 or 1,3 hydrogen shifts, however, starting with 2-phenylethyllithium (1) and 3-phenylpropyllithium (54), respectively, were not detected.With 3-phenylpropyllithium (54) a slow intramolecular 1,5 transfer an ortho proton is observed instead, yielding o-propylphenyllithium (100).The corresponding 1,6 shift with 4-phenylbutyllithium (2) was also detected in a minor amount in addition to the 1,4 proton shift already mentioned.There is no indication, however, for a 1,4 transfer of an ortho proton in 2-phenylethyllithium (1).The reaction products in this case can be exclusively explained by intermolecular transmetallation reactions.All ω-phenylalkyllithium compounds under investigation show interesting side and secondary reactions being rather different in deuterated solvents and in deuteriumfree solvents, respectively, due to the isotope effects.The analysis of the products is accomplished by 1H-NMR spectroscopy and, after derivatization, with the help of a GC-MS-combination.Stereoelectronic reasons are made responsible for the failure of the intramolecular 1,2 and 1,3 proton shift in these systems.
