19125-73-6Relevant academic research and scientific papers
Ruthenium-Catalyzed Isomerization of ortho-Silylanilines to Their para Isomers
Ishiga, Wataru,Ohta, Masaya,Kodama, Takuya,Tobisu, Mamoru
supporting information, p. 6714 - 6718 (2021/09/02)
The catalytic ortho to para transposition of a silyl group in aniline derivatives is described. [RuCl2(p-cymene)]2/BINAP in conjunction with a Cu(OAc)2 additive serves as a potent catalytic system. This method is also applicable to the isomerization of 2-silylpyrrole derivatives to the corresponding 3-silyl isomers.
A visible-light-photocatalytic water-splitting strategy for sustainable hydrogenation/deuteration of aryl chlorides
Ling, Xiang,Xu, Yangsen,Wu, Shaoping,Liu, Mofan,Yang, Peng,Qiu, Chuntian,Zhang, Guoqiang,Zhou, Hongwei,Su, Chenliang
, p. 386 - 392 (2020/02/25)
Hydrogenation/deuteration of carbon chloride (C?Cl) bonds is of high significance but remains a remarkable challenge in synthetic chemistry, especially using safe and inexpensive hydrogen donors. In this article, a visible-light-photocatalytic watersplitting hydrogenation technology (WSHT) is proposed to in-situ generate active H-species (i.e., Had) for controllable hydrogenation of aryl chlorides instead of using flammable H2. When applying heavy water-splitting systems, we could selectively install deuterium at the C?Cl position of aryl chlorides under mild conditions for the sustainable synthesis of high-valued added deuterated chemicals. Sub-micrometer Pd nanosheets (Pd NSs) decorated crystallined polymeric carbon nitrides (CPCN) is developed as the bifunctional photocatalyst, whereas Pd NSs not only serve as a cocatalyst of CPCN to generate and stabilize H (D)-species but also play a significant role in the sequential activation and hydrogenation/deuteration of C?Cl bonds. This article highlights a photocatalytic-WSHT for controllable hydrogenation/deuteration of low-cost aryl chlorides, providing a promising way for the photosynthesis of high-valued added chemicals instead of the hydrogen evolution.
A Path to More Sustainable Catalysis: The Critical Role of LiBr in Avoiding Catalyst Death and its Impact on Cross-Coupling
Eckert, Philip,Organ, Michael G.
, p. 4861 - 4865 (2020/04/30)
The role that LiBr plays in the lifetime of Pd-NHC complexes has been investigated. A bromide ion is proposed to coordinate to Pd thereby preventing beta hydride elimination (BHE) (to form NHC-H+) of the reductive elimination (RE) intermediate that normally completes with the desired cross-coupling catalytic cycle. Coordinating groups, such as anilines, are able to bind suitably well to Pd to prevent this pathway from occurring, thus reducing the need for the added salt. The metal hydride formed from BHE is very unstable and RE of the hydride to the NHC ligand occurs very rapidly giving rise to the corresponding hydrido-NHC (i.e., NHC-H+). The use of the per deuterated dibutylzinc shows a significant deuterium isotope effect, shutting down catalyst death almost completely. The use of bis-neopentylzinc, now possessing no hydrides, eliminates catalyst death all together leading to a very long-lived catalytic cycle and confirming the untoward role of BHE.
Rhodium-Catalyzed Transarylation of Benzamides: C-C Bond vs C-N Bond Activation
He, Shiyu,Long, Yang,Su, Zhishan,Xiang, Haifeng,Zheng, Yanling,Zhong, Jing,Zhou, Xiangge
, p. 3398 - 3403 (2020/03/23)
A rhodium-catalyzed transarylation of benzamides via selective C-C bond activation with arylboronic acids was described, which was distinct from the conventional metal-catalyzed C-N bond activation. This transformation exhibited good functional group compatibility with yields up to 88%, offering a practical approach for the construction and functionalization of benzamides. Preliminary experimental and computational studies revealed the selectivity of metal insertion into the C-C bond or the C-N bond was greatly affected by substituents on the amide's N atom.
Rhodium-Catalyzed Pyridine N-Oxide Assisted Suzuki-Miyaura Coupling Reaction via C(O)-C Bond Activation
Zhong, Jing,Long, Yang,Yan, Xufei,He, Shiyu,Ye, Runyou,Xiang, Haifeng,Zhou, Xiangge
, p. 9790 - 9794 (2019/12/24)
A rhodium-catalyzed Suzuki-Miyaura coupling reaction via C(O)-C bond activation to form 2-benzoylpyridine N-oxide derivatives is reported. Both the C(O)-C(sp2) and C(O)-C(sp3) bond could be activated during the reaction with yields up to 92%. The N-oxide moiety could be employed as a traceless directing group, leading to free pyridine ketones.
A preparing method of deuterated aromatic compounds
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Paragraph 0040; 0041, (2019/01/08)
The invention belongs to the field of chemical synthesis, particularly a preparing method of deuterated aromatic compounds. The method includes subjecting an aryl halide, as an initial raw material, to a palladium catalyzed carbon-halogen bond reduction r
