76481-36-2Relevant academic research and scientific papers
Access to "friedel-Crafts-Restricted" tert -alkyl aromatics by activation/methylation of tertiary benzylic alcohols
Hartsel, Joshua A.,Craft, Derek T.,Chen, Qiao-Hong,Ma, Ming,Carlier, Paul R.
experimental part, p. 3127 - 3133 (2012/05/20)
Herein we describe a two-step protocol to prepare m-tert-alkylbenzenes. The appropriate tertiary benzylic alcohols are activated with SOCl2 or concentrated HCl and then treated with trimethylaluminum, affording the desired products in 68-97% yields (22 examples). This reaction sequence is successful in the presence of a variety of functional groups, including acid-sensitive and Lewis-basic groups. In addition to t-Bu groups, 1,1-dimethylpropyl and 1-ethyl-1-methylpropyl groups can also be installed using this method.
Arene-catalysed lithiation of fluoroarenes
Guijarro, David,Yus, Miguel
, p. 1135 - 1138 (2007/10/03)
The reaction of different fluoroarenes 1 with lithium and a catalytic amount (7%) of naphthalene in THF at -30°C affords the corresponding aryllithium intermediates which, by reaction with several electrophiles at temperatures ranging between -30 and 0°C, lead to the expected products 2, after hydrolysis. (C) 2000 Elsevier Science Ltd.
Transition-State Polarization in Cleavage of C-C Bonds in Radical Anions
Maslak, Przemyslaw,Narvaez, Javier N.,Kula, Jozef,Malinski, David S.
, p. 4550 - 4559 (2007/10/02)
The substituent effect on the rate of C-C bond cleavage in radical anions of 1-(4-nitrophenyl)-2-(substituted-phenyl)-1,1,2,2-tetraethylethanes has been explored.The data provide evidence for two distinctive modes of bond scission.One mode is characterized by a significant negative charge transfer across the scissile bond in the transition state.Such polarization of the transition state is in contradiction to the prediction based on the fragments' stability.The second mode, dominant in cases where the charge shift leads to negative charge accumulation on an already electron-rich fragment, involves a ?* radical anion.Both modes point to a general kinetic preference for a cleavage of radical anions that allows for charge delocalization across the scissile bond.
