3141-93-3Relevant articles and documents
Regioselection in the synthesis of 4-benzyltetral-1-ones and the new 4-arylbenzosuber-1-ones
Truong, Daniel,Howard, Brittany L.,Thompson, Philip E.
, (2021/03/09)
The intramolecular Friedel-Crafts acylation of 4,5-diarylpentanoic acids has the possibility to cyclise to either a 6-membered ring to give 4-benzyltetral-1-one or a 7-membered ring to give 4-arylbenzosuber-1-one. Of these, only the former compound class has previously been reported. The impact of the substituents positioning on the outcome of the cyclisation has been investigated. The complete formation of either the tetralone or the benzosuberone regioisomer was possible under the same reaction conditions, dependent upon the ring activation and/or deactivation of the chosen substituents. Selected bromo or methoxy substituents could be used as auxiliaries, included in precursors to afford the desired regioisomer and then subsequently removed.
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.].
Rh(III)-catalyzed C-H activation/cyclization of oximes with alkenes for regioselective synthesis of isoquinolines
Chen, Renjie,Qi, Jifeng,Mao, Zhenjun,Cui, Sunliang
supporting information, p. 6201 - 6204 (2016/07/11)
A Rh(iii)-catalyzed C-H activation/cyclization of oximes and alkenes for facile and regioselective access to isoquinolines has been developed. This protocol features mild reaction conditions and easily accessible starting materials, and has been applied to the concise synthesis of moxaverine. A kinetic isotope effect study was conducted and a plausible mechanism was proposed.