16765-38-1Relevant academic research and scientific papers
Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
Velasco, Rocío,Silva López, Carlos,Nieto Faza, Olalla,Sanz, Roberto
, p. 15058 - 15068 (2016/10/11)
By carefully controlling the reaction temperature, treatment of aryl benzyl ethers with tBuLi selectively leads to α-lithiation, generating stable organolithiums that can be directly trapped with a variety of selected electrophiles, before they can undergo the expected [1,2]-Wittig rearrangement. This rearrangement has been deeply studied, both experimentally and computationally, with aryl α-lithiated benzyl ethers bearing different substituents at the aryl ring. The obtained results support the competence of a concerted anionic intramolecular addition/elimination sequence and a radical dissociation/recombination sequence for explaining the tendency of migration for aryl groups. The more favored rearrangements are found for substrates with electron-poor aryl groups that favor the anionic pathway.
GENERATION OF α-ACYLCARBENIUM IONS: A NOVEL UNCATTALYSED C-C BOND FORMATION AT ROOM TEMPERATURE
Kulkarni, Gururaj C.,Karmarkar, Sanjay N.,Kelkar, Shriniwas L.,Wadia, Murzban S.
, p. 5189 - 5198 (2007/10/02)
Reactions of substituted desyl chloride 1 and 5 with phenol at room temperature in benzene results in C-alkylation.The reaction is shown to proceed through a benzylic α-acylcarbenium ion.This contention is supported by (i) the failure of this reaction with haloketones 8 and 22 and (ii) the different nature of products obtained when these haloketones were allowed to react in the presence of K2CO3.
