605-05-0Relevant academic research and scientific papers
Diarylmethane compounds as well as preparation method and application thereof
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Paragraph 0139; 0143-0148; 0209-0214, (2019/08/20)
The invention discloses diarylmethane compounds as well as a preparation method and application thereof. The diarylmethane compounds have a molecular structural general formula as defined by a generalformula (I) in the description. The preparation method of the diarylmethane compounds comprises the steps of adding a benzyl halogenated hydrocarbon compound A and an arylboronic acid B into a reaction system containing an organic small-molecular catalyst, an alkali reagent and a solvent, and performing a reaction to prepare the compounds. The diarylmethane compounds provided by the invention contain electron withdrawing groups and an electron-donating group substituted diarylmethane basic structure, and can be widely used for synthesis of pharmaceutical intermediates, particularly polysubstituted methane compounds, and preparation of functional materials; and the preparation method has a simple process and low requirements for reaction conditions, the reaction process is safe and controllable, the atomic utilization rate and production efficiency are high, the regioselectivity and stereoselectivity of the products are efficiently ensured, a frontier science small-molecule organocatalysis concept is introduced, and the method is friendly to the environment.
Pd(II)-NHDC-Functionalized UiO-67 Type MOF for Catalyzing Heck Cross-Coupling and Intermolecular Benzyne-Benzyne-Alkene Insertion Reactions
Wei, Yong-Liang,Li, Yue,Chen, Yun-Qi,Dong, Ying,Yao, Jia-Jia,Han, Xin-Yue,Dong, Yu-Bin
, p. 4379 - 4386 (2018/04/25)
A novel palladium N-heterocyclic bis-carbene dicarboxylate ligand (Pd-NHDC-H2L) was successfully synthesized. In addition, an Pd-NHDC-containing UiO-67 type MOF (UiO-67-Pd-NHDC) was prepared on the basis of a size-matched ligand mixture of biphenyl-4,4′-dicarboxylic acid/Pd-NHDC-H2L (9/1) and ZrCl4 under solvothermal conditions. The obtained UiO-67-Pd-NHC MOF can be a highly heterogeneous catalyst to promote Heck cross-coupling and intermolecular benzyne-benzyne-alkene insertion reactions.
Nickel-catalyzed cross-coupling of aldehydes with aryl halides: Via hydrazone intermediates
Tang, Jianting,Lv, Leiyang,Dai, Xi-Jie,Li, Chen-Chen,Li, Lu,Li, Chao-Jun
supporting information, p. 1750 - 1753 (2018/02/21)
Traditional cross-couplings require stoichiometric organometallic reagents. A novel nickel-catalyzed cross-coupling reaction between aldehydes and aryl halides via hydrazone intermediates has been developed, merging the Wolff-Kishner reduction and the classical cross-coupling reactions. Aromatic aldehydes, aryl iodides and aryl bromides are especially effective in this new cross-coupling chemistry.
Cross-Coupling of Phenol Derivatives with Umpolung Aldehydes Catalyzed by Nickel
Lv, Leiyang,Zhu, Dianhu,Tang, Jianting,Qiu, Zihang,Li, Chen-Chen,Gao, Jian,Li, Chao-Jun
, p. 4622 - 4627 (2018/05/22)
A nickel-catalyzed cross-coupling to construct the C(sp2)-C(sp3) bond was developed from two sustainable biomass-based feedstocks: phenol derivatives with umpolung aldehydes. This strategy features the in situ generation of moisture/air-stable hydrazones from naturally abundant aldehydes, which act as alkyl nucleophiles under catalysis to couple with readily available phenol derivatives. The avoidance of using both halides as the electrophiles and organometallic or organoboron reagents (also derived from halides) as the nucleophiles makes this method more sustainable. Water tolerance, great functional group (ketone, ester, free amine, amide, etc.) compatibility, and late-stage elaboration of complex biological molecules exemplified its practicability and unique chemoselectivity over organometallic reagents.
Gold(I)-catalyzed Benzylation of (Hetero)aryl Boronic Acids with (Hetero)benzyl Bromides by the Strategy of a SN2-type Reaction
Zang, Wenqing,Wei, Yin,Shi, Min
supporting information, p. 2791 - 2795 (2018/09/20)
Herein, the first example of gold-catalyzed benzylation of (hetero)aryl boronic acids with (hetero)benzyl bromides to give the corresponding cross-coupling products in moderate to good yields is reported. The reaction proceeds through a possible intermolecular SN2-type reaction pathway to give a wide variety of di(hetero)arylmethanes as the desired products. An intriguing reaction mechanism has been proposed on the basis of control experiments, 31P-NMR spectroscopic detection and DFT calculations.
Transition-Metal-Free Suzuki-Type Cross-Coupling Reaction of Benzyl Halides and Boronic Acids via 1,2-Metalate Shift
He, Zhiqi,Song, Feifei,Sun, Huan,Huang, Yong
supporting information, p. 2693 - 2699 (2018/02/28)
Cross-coupling of organoboron compounds with electrophiles (Suzuki-Miyaura reaction) has greatly advanced C-C bond formation and has been well received in medicinal chemistry. During the past 50 years, transition metals have played a central role throughout the catalytic cycle of this important transformation. In this process, chemoselectivity among multiple carbon-halogen bonds is a common challenge. In particular, selective oxidative addition of transition metals to alkyl halides rather than aryl halides is difficult due to unfavorable transition states and bond strengths. We describe a new approach that uses a single organic sulfide catalyst to activate both C(sp3) halides and arylboronic acids via a zwitterionic boron "ate" intermediate. This "ate" species undergoes a 1,2-metalate shift to afford Suzuki coupling products using benzyl chlorides and arylboronic acids. Various diaryl methane analogues can be prepared, including those with complex and biologically active motifs. The reactions proceed under transition-metal-free conditions, and C(sp2) halides, including aryl bromides and iodides, are unaffected. The orthogonal chemoselectivity is demonstrated in the streamlined synthesis of highly functionalized diaryl methane scaffolds using multi-halogenated substrates. Preliminary mechanistic experiments suggest both the sulfonium salt and the sulfur ylide are involved in the reaction, with the formation of sulfonium salt being the slowest step in the overall catalytic cycle.
An Efficient Synthetic Approach to trans-(NHC)2Pd(R)Br Type Complexes and Their Use in Suzuki–Miyaura Cross-Coupling Reactions
Kumar, Anuj,Prakasham,Gangwar, Manoj Kumar,Vishnoi, Pratap,Butcher, Raymond J.,Ghosh, Prasenjit
, p. 2144 - 2154 (2017/04/21)
Mixed organohalidopalladium complexes of the type trans-(NHC)2Pd(R)Br were conveniently obtained from trans-(NHC)2PdBr2 type complexes by a ligand-substitution reaction. In particular, the trans-[1-(1S)-menthyl-4-(R1)-1,2,4-triazol-5-ylidene]2Pd(R2)Br [R1 = Et, R2 = CH2Ph (3a1); R1 = Et, R2 = o-OMeC6H4 (3a2); R1 = R2 = CH2Ph (3b1); R1 = CH2Ph, R2 = o-OMeC6H4 (3b2)] complexes were obtained from the corresponding palladium(II) precursor complexes, 2a,b, by reaction with the respective Grignard reagents, in good to excellent yields (74–93 %). Three of the four mixed organohalidopalladium complexes, 3a1,a2,b1, have been structurally characterized by single-crystal X-ray diffraction, which revealed the trans disposition of the NHC ligands around the palladium center. The use of these mixed organohalidopalladium complexes in the Suzuki–Miyaura cross-coupling reaction was established for all of the complexes, 3a1–b2, which yielded the desired cross-coupled products upon treatment with various ArB(OH)2 [Ar = 1-naphthyl, 4-(1,1′-biphenyl), 9-phenanthrenyl, 4-FC6H4, and 2,6-Me2C6H3] compounds, in the presence of NaOH as a base, in CH3CN, in three hours, under reflux conditions.
Direct cross-coupling of benzyl alcohols to construct diarylmethanes via palladium catalysis
Cao, Zhi-Chao,Yu, Da-Gang,Zhu, Ru-Yi,Wei, Jiang-Bo,Shi, Zhang-Jie
supporting information, p. 2683 - 2686 (2015/03/05)
A direct arylation to furnish diarylmethanes from benzyl alcohols was realized through Pd(PPh3)4-catalyzed Suzuki-Miyaura coupling via benzylic C-O activation in the absence of any additives. The arylation is compatible with various functional groups. This development provides an atom- and step-economic way to approach a diarylmethane scaffold under mild and environmentally benign conditions. This journal is
Synthesis of phenanthrenes through copper-catalyzed cross-Coupling of N-tosylhydrazones with terminal alkynes
Hossain, Mohammad Lokman,Ye, Fei,Liu, Zhenxing,Xia, Ying,Shi, Yi,Zhou, Lei,Zhang, Yan,Wang, Jianbo
, p. 8689 - 8699 (2015/01/08)
A novel protocol for the synthesis of phenanthrenes through the copper-catalyzed reaction of aromatic tosylhydrazones with terminal alkynes is explored. The reaction proceeds via the formation of an allene intermediate and subsequent six-π-electron cyclization-isomerization, affording phenanthrene derivatives in good yields. The transformation can be performed in two ways:(1)with Ntosylhydrazones derived from [1,1'-biphenyl]-2-carbaldehydes and terminal alkynes as the starting materials and(2)with Ntosylhydrazones derived from aromatic aldehydes and 2-alkynyl biphenyls as the starting materials. This new phenanthrene synthesis uses readily available starting materials and a cheap copper catalyst and has a wide range of functional group compatibility.
Expedient synthesis of phenanthrenes via In(III)-catalyzed 6-exo-dig cycloisomerization
Kwon, Yongseok,Cho, Hyunkyung,Kim, Sanghee
, p. 920 - 923 (2013/03/28)
This paper documents the first example of In(III)-catalyzed selective 6-exo-dig hydroarylation of o-propargylbiaryls and their subsequent double-bond migration to obtain functionalized phenanthrenes. Electron-rich biaryl substrates undergo hydroarylation
