37155-52-5Relevant academic research and scientific papers
Cross-coupling reaction of allylic and benzylic carbonates with organo[2-(hydroxymethyl)phenyl]dimethylsilanes
Nakao, Yoshiaki,Ebata, Shiro,Chen, Jinshui,Imanaka, Hidekazu,Hiyama, Tamejiro
, p. 606 - 607 (2007)
The title reaction is found to proceed in the presence of a palladium catalyst and in the absence of any activator. Various functional groups are tolerated to give a diverse range of 1,4-diene and diarylmethane products, which are ubiquitous units of natural products and pharmaceuticals. Copyright
Method for synthesizing diaryl methane derivative
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Paragraph 0013; 0048-0049, (2021/09/21)
The invention aims to provide a method for synthesizing a diaryl methane derivative. The method is characterized in that tris (dibenzylideneacetone) dipalladium is used as a catalyst, an organic antimony compound is used as a nucleophilic reagent, benzyl bromide and benzyl chloride are used as electrophilic reagents, toluene is used as a solvent, and the diaryl methane derivative is synthesized through direct cross coupling under the air atmosphere condition. The method has the characteristics of good substrate universality, good functional group tolerance, simplicity and convenience in operation and the like.
Nickel catalyzed deoxygenative cross-coupling of benzyl alcohols with aryl-bromides
Kumar Chenniappan, Vinoth,Peck, Devin,Rahaim, Ronald
supporting information, (2020/03/03)
A nickel-catalyzed cross-electrophile coupling of benzyl alcohols with aromatic bromides has been developed. This deoxygenative cross-coupling occurs under mild reaction conditions at ambient temperature affording diarylmethanes, or 1,3-diarylpropenes from benzyl allyl alcohols. The system demonstrated good chemoselectivity tolerating an assortment of reactive functional groups.
Cobalt-Catalyzed Formation of Functionalized Diarylmethanes from Benzylmesylates and Aryl Halides
Reddy, Bhoomireddy Rajendra Prasad,Chowdhury, Sushobhan,Auffrant, Audrey,Gosmini, Corinne
, p. 3026 - 3029 (2018/08/24)
A simple cobalt-catalyzed reductive coupling protocol allowing the synthesis of functionalized diarylmethanes from benzyl mesylate is described. The possibility to directly use the benzyl alcohol as a result of a two-step reaction is also presented. This method tolerates a variety of functional groups. A benzyl radical is likely involved. (Figure presented.).
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.
Palladium-Catalysed Cross-Coupling of Benzylammonium Salts with Boronic Acids under Mild Conditions
Türtscher, Paul L.,Davis, Holly J.,Phipps, Robert J.
, p. 793 - 803 (2017/10/07)
Herein, we give a full account of the development of the palladium-catalysed cross-coupling of benzylammonium salts with boronic acids. A range of benzylamine-derived quaternary ammonium salts can be coupled with boronic acids under relatively mild conditions. Our optimization has identified ligands that can be used to chemoselectively cross-couple at the ammonium in the presence of chlorides. We demonstrate that intramolecular palladium-catalysed C-H activation is also a viable pathway for the putative benzyl-Pd(II) intermediate obtained upon oxidative addition and have optimised this to obtain fluorene in good yield.
Benzylation of arenes with benzyl halides synergistically promoted by in situ generated superacid boron trifluoride monohydrate and tetrahaloboric acid
Huang, Ruofeng,Zhang, Xiaohui,Pan, Jing,Li, Jiaqiang,Shen, Hang,Ling, Xuege,Xiong, Yan
supporting information, p. 1540 - 1546 (2015/03/04)
To examine the assembly methodology of diarylmethanes, a benzylation of (hetero)arenes with benzyl halides has been developed and various diarylmethanes were furnished with yields of up to 98% and regioselectivities of up to >99%. The complexation of the by-product halogen hydride with BF3·OEt2 generated the Bronsted acid BF3·HX (HBF3X, X=Cl or Br) in situ to synergistically promote the benzylation.
Iodine-catalyzed disproportionation of aryl-substituted ethers under solvent-free reaction conditions
Jereb, Marjan,Vrazic, Dejan
, p. 1978 - 1999 (2013/05/22)
Iodine was demonstrated to be an efficient catalyst for disproportionation of aryl-substituted ethers under solvent-free reaction conditions. Variously substituted 1,1,1′,1′-tetraaryldimethyl ethers were transformed into the corresponding diarylketone and diarylmethane derivatives. I 2-catalyzed transformation of 4-methoxyphenyl substituted ethers yielded mono- and dialkylated Friedel-Crafts products as well. Treatment of trityl alkyl and trityl benzyl ethers with a catalytic amount of iodine produced triphenylmethane and the corresponding aldehydes and ketones. The electron-donating substituents facilitated the reaction, while the electron-withdrawing groups retarded it; the difference in reactivity is not very high. Such an observation may be in favour of hydride transfer, predominantly from the less electron rich side of the ether with more stable carbocation formation. With the isotopic studies it was established that a substantial portion of the C-H bond scission took place in the rate-determining step, while the carbonyl oxygen atom originated from the starting ether, and not from the air. The transformation took place under air and under argon, and HI was not a functioning catalyst.
Highly efficient method for solvent-free synthesis of diarylmethane and triarylmethane from benzylic alcohols using P2O5/Al 2O3 or P2O5/SiO2 at room temperature
Khazaei, Ardeshir,Rad, Mohammad Navid Soltani,Borazjani, Maryam Kiani,Moradian, Khadijeh Mansouri,Borazjani, Mohammad Kiani,Zebarjadian, Mohammad Hassan
experimental part, p. 120 - 126 (2012/06/18)
A highly efficient procedure for the synthesis of triarylmethane and diarylmethane via benzylation of aromatic hydrocarbons from benzyl alcohols using supported P2O5 on SiO2 and/or Al 2O3 under solvent-free conditions is described. Excellent yields of triarylmethane and diarylmethane were obtained using P 2O5-SiO2 (50%W/W) and/or P2O 5-Al2O3 (50%W/W) at room temperature. The reusability of both supported P2O5 on SiO2 and Al2O3 were examined. Both supported reagents show favorable activities in first and second runs, however, a decline in reactivity was observed in following attempts. The reaction is scalable to > 0.03 mole amounts.
Cross-coupling of grignard reagents with sulfonyl-activated sp3 carbon-nitrogen bonds
Li, Man-Bo,Tang, Xiang-Ling,Tian, Shi-Kai
experimental part, p. 1980 - 1984 (2011/10/12)
Sulfonyl-activated sp3 carbon-nitrogen bonds have been found to be cleaved by Grignard reagents in the presence of 5 mol% of copper(I) iodide (CuI). Significantly, a broad range of sulfonyl-activated benzylic, allylic, and propargylic amines smoothly undergo the cross-coupling reaction with Grignard reagents to afford structurally diverse coupling products in good to excellent yields and with high chemo-, regio-, and stereoselectivity. Moreover, an S N2 mechanism has been demonstrated to be involved in the cross-coupling reaction that allows the asymmetric synthesis of chiral hydrocarbons from optically active α-branched amine derivatives. Copyright
