133383-81-0Relevant articles and documents
Microsolvation, aggregation, and pseudomonomolecular, ionic sp 2-stereoinversion mechanism of two exocyclic β,β-di-tert- alkyl-α-arylvinyllithiums This article is dedicated to Professor Paul Knochel in recognition of his kind support.
Knorr, Rudolf,Hennig, Karsten-Olaf,B?hrer, Petra,Schubert, Bernhard
, p. 125 - 135 (2014)
A THF-solvated, crystalline, exocyclic alkenyllithium, (tert-alkyl) 2CC(Li)-Ph, was synthesized and shown to be a disolvated dimer in the solid state and in toluene as the solvent; increasing amounts of the monomeric species emerged on cooling the toluene solution. In THF as the solvent, only the trisolvated monomer was present and identified as a contact ion pair (CIP) through its scalar 13C,6Li NMR coupling. This ground-state needs only one further THF ligand as a catalyst for breaking the C-Li bond with formation of a tetrasolvated, solvent-separated ion pair (SSIP) on the way to the transition state of cis/trans sp2-stereoinversion. The ensuing pseudomonomolecular, ionic mechanism is confirmed by low pseudoactivation parameters: enthalpy ΔHψ? = 6.9(3) kcal mol-1; entropy ΔSψ? = -23.3(9) cal mol-1 K-1. Similar parameters were found with 2,6-dimethylphenyl in place of Ph.
Aluminium-mediated [4 + 1] cyclization reaction: Novel synthesis of 2,2,5,5-tetramethylcyclopentanecarboxylic acid
Reddy,Hanamoto,Hiyama
, p. 521 - 524 (2007/10/02)
A new [4 + 1] cyclization reaction mediated by aluminium is developed and applied to the synthesis of 2,2,5,5-tetramethylcyclopentanecarboxylic acid, a part of an artificial sweetner.