- Homologation of Electron-Rich Benzyl Bromide Derivatives via Diazo C-C Bond Insertion
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The ability to manipulate C-C bonds for selective chemical transformations is challenging and represents a growing area of research. Here, we report a formal insertion of diazo compounds into the "unactivated"C-C bond of benzyl bromide derivatives catalyzed by a simple Lewis acid. The homologation reaction proceeds via the intermediacy of a phenonium ion, and the products contain benzylic quaternary centers and an alkyl bromide amenable to further derivatization. Computational analysis provides critical insight into the reaction mechanism, in particular the key selectivity-determining step.
- Modak, Atanu,Alegre-Requena, Juan V.,De Lescure, Louis,Rynders, Kathryn J.,Paton, Robert S.,Race, Nicholas J.
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supporting information
p. 86 - 92
(2021/12/27)
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- Lessons from an Array: Using an Electrode Surface to Control the Selectivity of a Solution-Phase Chemical Reaction
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Electrochemistry offers a variety of novel means by which selectivity can be introduced into synthetic organic transformations. In the work reported, it is shown how methods used to confine chemical reactions to specific sites on a microelectrode array can also be used to confine a preparative reaction to the surface of an electrode inserted into a bulk reaction solution. In so doing, the surface of a modified electrode can be used to introduce new selectivity into a preparative reaction that is not observed in the absence of either the modified electrode surface or the effort to confine the reaction to that surface. The observed selectivity can be optimized in the same way that confinement is optimized on an array and is dependent on the nature of the functionalized surface.
- Feng, Enqi,Jing, Qiwei,Moeller, Kevin D.
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supporting information
(2022/01/26)
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- Controlled Reduction of Carboxamides to Alcohols or Amines by Zinc Hydrides
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New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX2). Use of a different halide on ZnX2 dictates the selectivity, wherein the NaH-ZnI2 system delivers alcohols and NaH-ZnCl2 gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH2)∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)2 is the key species for the production of amines.
- Ong, Derek Yiren,Yen, Zhihao,Yoshii, Asami,Revillo Imbernon, Julia,Takita, Ryo,Chiba, Shunsuke
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p. 4992 - 4997
(2019/03/13)
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- Preparation method for chlorbipram PDE4-inhibitor
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The invention discloses a preparation method for a chlorbipram PDE4-inhibitor. The method is capable of using 3-bromine-4-methoxybenzaldehyde as a starting raw material, and synthesizing a target product of E chlorbipram by steps, such as reduction reacti
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Paragraph 0024-0025
(2017/08/23)
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- A photo-induced C-O bond formation methodology to construct tetrahydroxanthones
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A metal-free, photo-induced C-O bond formation methodology was developed to construct tetrahydroxanthones. This mild and efficient methodology was based on intramolecular oxygen trapping of the reactive species produced by photolytic activation of a C-Cl
- Xiao, Zheming,Cai, Shujun,Shi, Yingbo,Yang, Baochao,Gao, Shuanhu
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supporting information
p. 5254 - 5257
(2014/05/06)
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- A concise synthesis of biaryl PDE4D allosteric modulators
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The optimization and synthesis of biaryl PDE4D allosteric modulator D159687 was achieved on gram scale via a concise two-step process. The synthesis features sequential chemoselective Suzuki coupling reactions taking advantage of different reactivity prof
- Dalby, Amy,Mo, Xuesheng,Stoa, Robert,Wroblewski, Nathaniel,Zhang, Zheng,Hagen, Timothy J.
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p. 2737 - 2739
(2013/06/05)
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- Total synthesis of acerogenins E, G and K, and centrolobol
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The first total synthesis of the diarylheptanoid acerogenins E and K, isolated from Acer nikoense MAXIM., is described. Formation of the 13-membered m,m-cyclophane skeleton was successfully achieved on the basis of a domino process involving a Miyaura arylborylation-intramolecular Suzuki reaction. The cyclization precursor was prepared via a Wittig reaction and Claisen-Schmidt condensation, which proceeded in moderate yields. The total synthesis of acerogenin G and centrolobol was also achieved from a common synthetic intermediate.
- Ogura, Tetsuhiro,Usuki, Toyonobu
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p. 2807 - 2815
(2013/03/28)
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- 1,2,3-Triazole analogs of combretastatin A-4 as potential microtubule-binding agents
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A series of cis-restricted 1,4- and 1,5-disubstituted 1,2,3-triazole analogs of combretastatin A-4 (1) have been prepared. Cytotoxicity and tubulin inhibition studies showed that 2-methoxy-5-((5-(3,4,5-trimethoxyphenyl)-1H-1,2, 3-triazol-1-yl)methyl)aniline (5e) and 2-methoxy-5-(1-(3,4,5-trimethoxybenzyl)- 1H-1,2,3-triazol-5-yl)aniline (6e) were two of the most active compounds. Molecular modeling studies revealed that the N-2 and N-3 atoms in the triazole rings in 5e and 6e did not form hydrogen bonds with the amino acids in the anticipated pharmacophore.
- Odlo, Kristin,Fournier-Dit-Chabert, Jérémie,Ducki, Sylvie,Gani, Osman A.B.S.M.,Sylte, Ingebrigt,Hansen, Trond Vidar
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experimental part
p. 6874 - 6885
(2010/10/19)
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- The conversion of phenols to the corresponding aryl halides under mild conditions
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Mild, novel procedures have been developed for the syntheses of aryl halides from the corresponding phenols in modest to good yields via boronate ester intermediates.
- Thompson, Alicia L. S.,Kabalka, George W.,Akula, Murthy R.,Huffman, John W.
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p. 547 - 550
(2007/10/03)
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- ALYKYLENE DERIVATIVE HAVING EDG RECEPTOR ANTAGONISM
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PROBLEM TO BE SOLVED: To provide novel compounds having EDG (endothelial differentiation gene) receptor antagonism which are useful as active components of drugs for preventing and/or treating inflammatory diseases or the like. SOLUTION: The compounds are represented by formula (I) (wherein R1 is hydrogen or an alkyl group; R2 is hydrogen present at any substitutable position on ring C or a substituent such as a hydroxy group, a carboxy group, and a nitro group; R3 is hydrogen present at any substitutable position on ring D or a substitutent such as a hydroxy group and an aralkyloxy group; X is an alkylamino group, an amino group or the like; Y is a carboxy group, a sulfo group or a phosphono group; Z is oxygen, sulfur or the like; a ring represented by A is a 5- or 6-membered saturated or unsaturated hydrocarbon ring; and a ring represented by B is a 4- or 7-membered saturated or unsaturated hydrocarbon ring containing one -C=C- as a partial structure shown in the above formula) and include their salts and their esters.
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Page/Page column 106
(2010/02/12)
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- Imidazopyridinone derivatives and their use as phosphodiesterase inhibitors
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A compound (Ia): wherein the variables are defined in the specification, its prodrug or a pharmaceutically acceptable salt thereof useful in the treatment of angina, hypertension etc.
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- Uncatalysed hydrogen-transfer reductions of aldehydes and ketones
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Aldehydes and ketones are reduced to the corresponding alcohols by transfer hydrogenation at high temperature with EtOH, Pr(n)OH or Pr(i)OH as hydrogen donors in the absence of catalysts and base.
- Bagnell, Laurence,Strauss, Christopher R.
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p. 287 - 288
(2007/10/03)
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