1712-70-5Relevant articles and documents
Selective Synthesis of Substituted Pyridines and Pyrimidines through Cascade Annulation of Isopropene Derivatives
Chen, Lu,He, Runfa,Huang, Yubing,Li, Jiaming,Li, Jian,Li, Yibiao,Liu, Jiasheng,Liu, Yang
supporting information, p. 1620 - 1625 (2022/03/14)
Diverse substituted pyridines and pyrimidines with high selectivity were obtained using a concise and efficient protocol developed herein. The reaction proceeds via metal-free cascade annulation of isopropene derivatives. Using isopropene derivatives as C3 synthons, NH4I as the “N” source, and formaldehyde or dimethyl sulfoxide as the carbon source, this reaction realizes the efficient formation of intermolecular C-N and C-C bonds.
Metal-Free Deoxygenation of Chiral Nitroalkanes: An Easy Entry to α-Substituted Enantiomerically Enriched Nitriles
Pirola, Margherita,Faverio, Chiara,Orlandi, Manuel,Benaglia, Maurizio
supporting information, p. 10247 - 10250 (2021/06/18)
A metal-free, mild and chemodivergent transformation involving nitroalkanes has been developed. Under optimized reaction conditions, in the presence of trichlorosilane and a tertiary amine, aliphatic nitroalkanes were selectively converted into amines or nitriles. Furthermore, when chiral β-substituted nitro compounds were reacted, the stereochemical integrity of the stereocenter was maintained and α-functionalized nitriles were obtained with no loss of enantiomeric excess. The methodology was successfully applied to the synthesis of chiral β-cyano esters, α-aryl alkylnitriles, and TBS-protected cyanohydrins, including direct precursors of four active pharmaceutical ingredients (ibuprofen, tembamide, aegeline and denopamine).
1,3-Difunctionalization of β-alkyl nitroalkenes via combination of Lewis base catalysis and radical oxidation
Wang, Ye,Zheng, Lei,Shi, Xiaodong,Chen, Yunfeng
supporting information, p. 886 - 889 (2021/02/01)
Upon treatment with a Lewis base catalyst, β-alkyl-substituted nitroalkenes could be readily converted into allylic nitro compounds. Examples of either C-1 or C-3 functionalization methods have been reported through nitro-elimination, giving alkene products. In this work, successful 1,3-difunctionalization was achieved through a synergetic Lewis base catalysis and TBHP radical oxidation, giving vinylic alkoxyamines in good to excellent yields. This work further extended the general synthetic application of β-alkyl nitroalkenes.
Visible-Light-Induced Meerwein Fluoroarylation of Styrenes
Tang, Hai-Jun,Zhang, Bin,Xue, Fei,Feng, Chao
supporting information, p. 4040 - 4044 (2021/05/26)
An unprecedented approach for assembling a broad range of 1,2-diarylethane derivatives with fluorine-containing fully substituted carbon centers was developed. The protocol features straightforward operation, proceeds under metal-free condition, and accommodates a large variety of synthetically useful functionalities. The critical aspect to the success of this novel transformation lies in using aryldiazonium salts as both aryl radical progenitor and also as single electron acceptor which elegantly enables a radical-polar crossover manifold.
Enantioselective Hydrothiolation: Diverging Cyclopropenes through Ligand Control
Dong, Vy M.,Kuker, Erin L.,Lu, Alexander,Nie, Shaozhen
supporting information, p. 6176 - 6184 (2021/05/07)
In this article, we advance Rh-catalyzed hydrothiolation through the divergent reactivity of cyclopropenes. Cyclopropenes undergo hydrothiolation to provide cyclopropyl sulfides or allylic sulfides. The choice of bisphosphine ligand dictates whether the pathway involves ring-retention or ring-opening. Mechanistic studies reveal the origin for this switchable selectivity. Our results suggest the two pathways share a common cyclopropyl-Rh(III) intermediate. Electron-rich Josiphos ligands promote direct reductive elimination from this intermediate to afford cyclopropyl sulfides in high enantio- A nd diastereoselectivities. Alternatively, atropisomeric ligands (such as DTBM-BINAP) enable ring-opening from the cyclopropyl-Rh(III) intermediate to generate allylic sulfides with high enantio- A nd regiocontrol.
Palladium-Catalyzed Markovnikov Hydroaminocarbonylation of 1,1-Disubstituted and 1,1,2-Trisubstituted Alkenes for Formation of Amides with Quaternary Carbon
Yang, Hui-Yi,Yao, Ya-Hong,Chen, Ming,Ren, Zhi-Hui,Guan, Zheng-Hui
supporting information, p. 7298 - 7305 (2021/05/26)
Hydroaminocarbonylation of alkenes is one of the most promising yet challenging methods for the synthesis of amides. Herein, we reported the development of a novel and effective Pd-catalyzed Markovnikov hydroaminocarbonylation of 1,1-disubstituted or 1,1,2-trisubstituted alkenes with aniline hydrochloride salts to afford amides bearing an α quaternary carbon. The reaction makes use of readily available starting materials, tolerates a wide range of functional groups, and provides a facile and straightforward approach to a diverse array of amides bearing an α quaternary carbon. Mechanistic investigations suggested that the reaction proceeded through a palladium hydride pathway. The hydropalladation and CO insertion are reversible, and the aminolysis is probably the rate-limiting step.
Ni-Catalyzed Reductive Allylation of α-Chloroboronates to Access Homoallylic Boronates
Lou, Yixian,Qiu, Jian,Yang, Kai,Zhang, Feng,Wang, Chenglan,Song, Qiuling
supporting information, p. 4564 - 4569 (2021/06/28)
The transition-metal-catalyzed allylation reaction is an efficient strategy for the construction of new carbon-carbon bonds alongside allyl or homoallylic functionalization. Herein we describe a Ni-catalyzed reductive allylation of α-chloroboronates to efficiently render the corresponding homoallylic boronates, which could be readily converted into valuable homoallylic alcohols or amines or 1,4-diboronates. This reaction features a broad substrate scope with good functional group compatibility that is complementary to the existing methods for the preparation of homoallylic boronates.
Visible-light-promoted radical alkylation/cyclization of allylic amide with N-hydroxyphthalimide ester: Synthesis of oxazolines
Ding, Hao,Huang, Panyi,Jin, Can,Su, Weike,Sun, Bin,Yan, Zhiyang,Zhao, Haiyun
supporting information, (2021/10/29)
An efficient photocatalytic alkylation/cyclization of allylic amide with N-hydroxyphthalimide ester has been developed. The transformation is taken advantage of alkyl radicals to attack allylic amide with the assist of inexpensive rose bengal as photocatalyst to prepare a series of alkyl substituted oxazolines in moderate to excellent yields. High regioselectivity, operational safety, mild conditions and excellent substrate generality give this protocol broad application prospects.
MnBr2 catalyzed regiospecific oxidative Mizoroki-Heck type reaction
Chen, Xiang,Chen, Yi-Hung,Liu, Shanshan,Shen, Xiao,Zhu, Zhihong
supporting information, (2021/11/27)
Herein, we report an unprecedented regiospecific oxidative Mizoroki-Heck type reaction for the synthesis of ɑ-difluoromethyl homoallylic alcohols. The reaction shows broad substrate scopes and high functional group tolerance. Late-stage functionalization of complex biologically active molecules demonstrates the synthetic potential of this transformation. Mechanistic study supports the involvement of MnBr2 catalyzed radical 1,2-silyl transfer.
3 -trifluoromethyl -5 - aryl -1, 6 -dihydropyridazine compound and preparation method thereof (by machine translation)
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Paragraph 0048-0049; 0054-0055, (2020/08/25)
The invention relates to 3 - trifluoromethyl -5 - aryl -1, 6 -dihydropyridazine compound, and the structural formula of the compound is as follows. Ar refers to Ar. . . One of the following. , The invention also discloses a preparation method of the compound. To the invention, the oxidation/cyclization reaction of 4 - aryl substituted trifluoromethylhomoallylhydrazine is promoted by copper acetate, 3 - trifluoromethyl -5 - aryl -1 and 6 -dihydropyridazine compound with obvious aggregation-induced emission effect are obtained. (by machine translation)
