34663-15-5Relevant academic research and scientific papers
Efficient One-Pot Multifunctionalization of Alkynes en Route to α-Alkoxyketones, α-Thioketones, and α-Thio Thioketals by using an Umpolung Strategy
Xu, Zhou,Zhai, Rongliang,Liang, Ting,Zhang, Liming
supporting information, p. 14133 - 14137 (2017/10/16)
The use of polarized synthons is a highly desirable strategy, as it generally enables unprecedented retrosynthetic disconnections for the synthesis of unique substances. Herein, a new approach for α-oxygenated ketones, α-thioketones and α-thio thioketals via an intermolecular umpolung reaction between nucleophiles (alcohols/thioalcohols) and N-alkenoxypyridinium salts, which were generated from the corresponding alkynes, has been developed for the first time. The reactions proceed with good substrate scope and excellent functional group tolerance in one-pot manner. Applications of the products, α-oxygenated ketones, to the synthesis of other valuable synthetic moieties has also been successfully achieved.
One-pot synthesis of benzene-fused medium-ring ketones: Gold catalysis-enabled enolate umpolung reactivity
Xu, Zhou,Chen, Hongyi,Wang, Zhixun,Ying, Anguo,Zhang, Liming
, p. 5515 - 5518 (2016/05/24)
Enolate umpolung reactivities offer valuable and potentially unique alternatives over the enolate counterparts for the construction of ubiquitous carbonyl compounds. We disclose here that N-alkenoxypyridinium salts, generated readily upon gold-catalyzed additions of protonated pyridine N-oxide to C-C triple bonds of unactivated terminal alkynes, display versatile enolate umpolung chemistry upon heating and react with tethered arene nucleophiles in an SN2′ manner. In a synthetically efficient one-pot, two-step process, this chemistry enables expedient preparation of valuable benzo-fused seven-/eight-membered cyclic ketones, including those of O-/Nheterocycles, from easily accessible aryl-substituted linear alkyne substrates. The reaction yields can be up to 87%.
New Method for Generation of β-Oxido Carbenoid via Ligand Exchange Reaction of Sulfoxides: A Versatile Procedure for One-Carbon Homologation of Carbonyl Compounds
Satoh, Tsuyoshi,Itoh, Norifumi,Gengyo, Kaoru,Takada, Sae,Asakawa, Naoyuki,et al.
, p. 11839 - 11852 (2007/10/02)
A new procedure for one-carbon homologation of carbonyl compounds is described.The method is based on the rearrangement of β-oxido carbenoid which is generated via the ligand exchange reaction of the sulfinyl group of α-chloro β-hydroxy sulfoxide with tert-butyllithium.Addition of the carbanion of aryl 1-chloroalkyl sulfoxides to carbonyl compounds gave the adducts in good yields.The β-oxido carbenoid rearrangement of the adducts gave one-carbon homologated carbonyl compounds having an α-alkyl substituent.A similar reaction of the adducts derived from carbonyl compounds with chloromethyl p-tolyl sulfoxide yielded a procedure for a methylene insertion.The stereochemistry of the β-oxido carbenoid rearrangenment is also discussed.
