65564-55-8Relevant articles and documents
Iridium-Catalyzed Diastereoselective and Enantioselective Allylic Substitutions with Acyclic α-Alkoxy Ketones
Jiang, Xingyu,Chen, Wenyong,Hartwig, John F.
supporting information, p. 5819 - 5823 (2016/05/09)
The asymmetric alkylation of acyclic ketones is a longstanding challenge in organic synthesis. Reported herein are diastereoselective and enantioselective allylic substitutions with acyclic α-alkoxy ketones catalyzed by a metallacyclic iridium complex to form products with contiguous stereogenic centers derived from the nucleophile and electrophile. These reactions occur between allyl methyl carbonates and unstabilized copper(I) enolates generated in situ from acyclic α-alkoxy ketones. The resulting products can be readily converted into enantioenriched tertiary alcohols and tetrahydrofuran derivatives without erosion of enantiomeric purity.
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.