14142-16-6Relevant articles and documents
Stoichiometric and Catalytic Inter- and Intramolecular Hydroamination of Terminal Alkynes by Frustrated Lewis Pairs
Mahdi, Tayseer,Stephan, Douglas W.
, p. 11134 - 11142 (2015)
Frustrated Lewis pairs (FLPs) based on sterically encumbered anilines and the Lewis acid B(C6F5)3 were found to react with terminal alkynes effecting intermolecular hydroamination affording iminium alkynylborate species of the form [RPhN-C(R′)Me][R′CCB(C6F5)3]. In these cases, the reagent ratio of borane, aniline, and alkyne is 1:1:2. These reactions could also be performed in an intramolecular fashion by using anilines with alkynyl substituents effecting cyclization reactions. The use of 10mol % B(C6F5)3 under a H2 atmosphere provides a one-pot synthesis of the pyrrolidine 12, the piperidines 13-15, the azepane 16, the isoindoline 17, and the benzoxazine 18. Frustrated but satisfied: B(C6F5)3 was used to effect the stoichiometric and catalytic hydroamination of terminal alkynes by substituted anilines. Both inter- and intramolecular systems were explored in this reactivity. The mechanism adheres to previously observed frustrated Lewis pair reactivity.
Catalyst-free photodecarbonylation ofortho-amino benzaldehyde
Li, Lamei,Wang, Songping,Wei, Wentao,Yan, Ming,Zhou, Jingwei
supporting information, p. 3421 - 3426 (2020/06/25)
It is almost a consensus that decarbonylation of the aldehyde group (-CHO) needs to not only be mediated by transition metal catalysts, but also requires severe reaction conditions (high temperature and long reaction time). In this work, inspired by the “conformational-selectivity-based” design strategy, we broke this consensus and discovered a catalyst-free photodecarbonylation of the aldehyde group. It revealed that decarbonylation can be easily achieved with visible light irradiation by introducing a tertiary amine into theortho-position of the aldehyde group. A diverse array of tertiary amines is tolerated by our photodecarbonylation under mild conditions. Furthermore, the (QM) computations of the mechanism and the experiments on well-designed special substrates revealed that our photodecarbonylation depends on the conformational specificity of the aldehyde group and tertiary amine, and occurs through an unusual [1,4]-H shift and a subsequent [1,3]-H shift.
Photo-induced dealdehyding method
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Paragraph 0048-0053; 0144-0149, (2020/06/16)
The invention provides a photo-induced dealdehyding method, and belongs to the technical field of organic synthesis. The photo-induced dealdehyding method comprises the following steps that a mixtureof a compound shown in the formula I and a solvent are reacted under an inert gas atmosphere and visible light irradiation, a dealdehyding product is obtained, and no photocatalyst is used in the whole process; wherein the structural formula of the formula I shown in the specification, R is a functional group and is selected from hydrogen, methyl, methoxyl, cyano, chlorine, bromine or fluorine. According to the photo-induced dealdehyding method, in the inert gas atmosphere, the compound shown in the formula (I) can be excited to generate carbon-oxygen bond homogeneous cracking through visiblelight irradiation, then free radical migration and double bond displacement are conducted, finally carbon monoxide is removed, aldehyde group removal is completed, no photocatalyst is needed in the whole process, operation is easy and convenient, and conditions are mild.