4842-45-9Relevant articles and documents
Iodide-Catalyzed Carbonylation-Benzylation of Benzyl Chlorides with Potassium Aryltrifluoroborates under Ambient Pressure of Carbon Monoxide
Han, Wei,Chen, Junjie,Jin, Fengli,Yuan, Xiaorong
, p. 369 - 374 (2018)
Tetra- N -butylammonium iodide (TBAI) catalyzed carbonylation-benzylation of unactivated benzyl chlorides with potassium aryltrifluoroborates using CO gas has been developed. This reaction is transition-metal free, is carried out under ambient pressure, and provides a wide range of 1,2,3-triarylpropan-1-one derivatives in high yields. The novel method represents a significant improvement over the traditional palladium-catalyzed carbonylation.
Benzylic aroylation of toluenes with unactivated tertiary benzamides promoted by directed ortho-lithiation
Bao, Can-Can,Luo, Yan-Long,Du, Hui-Zhen,Guan, Bing-Tao
, p. 1349 - 1354 (2021/07/12)
The deprotonative functionalization of toluenes, for their weak acidity, generally needs strong bases, thus leading to the requirement of harsh conditions and the generation of by-products. Direct nucleophilic acyl substitution reaction of amides with organometallic reagents could provide an ideal solution for ketone synthesis. However, the inert amides and highly reactive organometallic reagents bring great challenges for an efficient and selective synthetic approach. Herein, we reported an lithium diisopropylamide (LDA)-promoted benzylic aroylation of toluenes with unactivated tertiary benzamides, providing a direct and efficient synthesis of various aryl benzyl ketones. This process features a kinetic deprotonative functionalization of toluenes with a readily available base LDA. Mechanism studies revealed that the directed ortho-lithiation of the tertiary benzamide with LDA promoted the benzylic kinetic deprotonation of toluene and triggered the nucleophilic acyl substitution reaction with the amide. [Figure not available: see fulltext.].
Iron-Catalyzed Ligand Free α-Alkylation of Methylene Ketones and β-Alkylation of Secondary Alcohols Using Primary Alcohols
Alanthadka, Anitha,Bera, Sourajit,Banerjee, Debasis
, p. 11676 - 11686 (2019/10/02)
Herein, we demonstrate a general and broadly applicable catalytic cross coupling of methylene ketones and secondary alcohols with a series of primary alcohols to disubstituted branched ketones. A simple and nonprecious Fe2(CO)9 catalyst enables one-pot oxidations of both primary and secondary alcohols to a range of branched gem-bis(alkyl) ketones. A number of bond activations and formations selectively occurred in one pot to provide the ketone products. Coupling reactions can be performed in gram scale and successfully applied in the synthesis of an Alzehimer's drug. Alkylation of a steroid hormone can be achieved. A single catalyst enables sequential one-pot double alkylation to bis-hetero aryl ketones using two different alcohols. Preliminary mechanistic studies using an IR probe, deuterium labeling, and kinetic experiments established the participation of a borrowing-hydrogen process using Fe catalyst, and the reaction produces H2 and H2O as byproducts.