1570-95-2Relevant academic research and scientific papers
Effect of Temperature on Borane Reduction of Representative Malonic Acids
Choi, Yong M.,Emblidge, Robert W.,Kucharczyk, Norbert,Sofia, R. Duane
, p. 1194 - 1198 (1989)
The controlled reaction of phenylmalonic acid (1a) with borane-THF at appropriate temperature makes available (phenylmalonyldioxy)borane , which has been characterized.Reduction of 2a or of the corresponding acid 1a proceeds at 0 deg C at the same rate.The reaction, however, is incomplete, showing only 33percent product formed in 4 h.Diethylmalonic acid (1b), which possesses no α-hydrogen, and the (diethylmalonyldioxy)borane (2b) are reduced at the same rate to the corresponding cyclic dialkoxyborane 5b.These results suggest that the reduction proceeds through intermediate formation of 2.The rates of the borane reduction for a series of malonic acids (1a-h) have been systematically studied and compared at 0 deg C and at -20 deg C.The reductions of aromatic substituted malonic acids (1f-h) are quite sluggish with substantial (46-72percent) α-metalation occurring at 0 deg C.Aliphatic alkylmalonic acids (1d-e) are reduced in 24 h with 34-40percent of α-metalation.At -20 deg C, most malonic acids are completely reduced in times ranging from 24 h for aliphatic (1c-e) to 3 days for aromatic (1f-h) compounds, with only 2-24percent α-metalation.The reduction of 1b at either 0 deg C or -20 deg C is completed in 8 h.At an appropriate lower temperature the reduction successfully competes with the α-metalation.
Synthesis of 14C-felbamate
Magatti,Lauzon,Saluja,Wang
, p. 165 - 172 (1997)
14C-Felbamate, 2-[ring-U-14C]phenyl-1,3-propanediol-dicarbamate, (1), was synthesized. The carbon label was introduced into Felbamate using uniformly labelled diethyl 2-phenylmalonate as the starting material.
Novel highly potent and selective sigma1 receptor antagonists effectively block the binge eating episode in female rats
Del Bello, Fabio,Quaglia, Wilma,Cifani, Carlo,Di Bonaventura, Emanuela Micioni,Botticelli, Luca,Giorgioni, Gianfabio,Pavletic, Pegi,Piergentili, Alessandro,Bonifazi, Alessandro,Schepmann, Dirk,Vistoli, Giulio,Di Bonaventura, Maria Vittoria Micioni
, p. 3107 - 3116 (2020)
In this paper, the benzo-cracking approach was applied to the potent sigma1 (σ1) receptor antagonist 1 to afford the less conformationally constrained 1,3-dioxane derivatives 2 and 3. To evaluate the effect of the increase in the distance between the two hydrophobic structural elements that flank the basic function, the cis and trans diastereomers of 4 and 5 were also prepared and studied. Compounds 2 and 3 showed affinity values at the σ1 receptor significantly higher than that of the lead compound 1. In particular, 3 displayed unprecedented selectivity over the σ2 receptor, the phencyclidine site of the NMDA receptor, and opioid receptor subtypes, as well as over the dopamine transporter. Docking results supported the structure-activity relationship studies. Due to its interesting biological profile, derivative 3, selected for an in vivo study in a validated preclinical model of binge eating, was able to counteract the overeating of palatable food only in binging rats, without affecting palatable food intake in the control group and anxiety-like and depression-related behaviors in female rats. This result strengthened the involvement of the σ1 receptor in the compulsive-like eating behavior and supported the σ1 receptor as a promising target for the management of eating disorders.
Double-Stranded Helical Oligomers Covalently Bridged by Rotary Cyclic Boronate Esters
Iida, Hiroki,Ohmura, Kenji,Noda, Ryuta,Iwahana, Soichiro,Katagiri, Hiroshi,Ousaka, Naoki,Hayashi, Taku,Hijikata, Yuh,Irle, Stephan,Yashima, Eiji
, p. 927 - 935 (2017)
Novel double helices covalently bridged by cyclic boronate esters were synthesized from complementary dimers with an m-terphenyl backbone joined by a chiral or achiral phenylene linker bearing diethyl boronates and diols, respectively. The X-ray crystallographic analysis and variable-temperature NMR and circular dichroism measurements, along with theoretical calculations, revealed that the double helices function as a “molecular rotor” in which the cyclic boronate ester units rotate, yielding two stable rotamers at low temperatures. Moreover, our data indicates that the covalently bonded double helices can undergo a unique helix-inversion simultaneously with a rotational motion of the boronate esters.
Arylsilylation of Electron-Deficient Alkenes via Cooperative Photoredox and Nickel Catalysis
Zhang, Zhikun,Hu, Xile
, p. 777 - 782 (2020)
Carbosilylation of alkenes can be an efficient approach to the synthesis of organosilicon compounds. However, few general methods of carbosilylation are known. Here, we introduce a strategy for arylsilylation of electron-deficient terminal alkenes by combining photoredox-catalyzed silyl radical generation, innate reactivity of silyl radical with alkene, and Ni-catalyzed aryl-Alkyl cross-coupling. This cooperative photoredox and nickel catalysis operates under mild conditions. It employs readily available alkenes, aryl bromides, and silane as reagents, and it produces useful synthetic building blocks in a modular manner.
Synthetic method for non-urethane intermediate 2-phenyl-1,3-propylene glycol
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Paragraph 0023-0052, (2019/10/01)
The invention discloses a synthetic method for a non-urethane intermediate 2-phenyl-1,3-propylene glycol. The synthetic method is characterized in that the 2-phenyl-1,3-propylene glycol can be obtained through the reaction of 2-phenyl-malonate and a reducing agent; and a reaction process includes the following steps: 1) uniformly mixing the 2-phenyl-malonate, the reducing agent and a solvent S1 under a protection gas, controlling a reaction temperature to rise to 130-150 DEG C and pressure to rise to 2-4 atmospheric pressure, dropping an aqueous solution A, controlling the dropping time of theaqueous solution A to be 30-60 min, starting to drop an aqueous solution B when the dropping time of the aqueous solution A arrives 5-8 min, controlling the dropping time of the aqueous solution B tobe 10-12 min, adding a solvent S2 after the adding of the aqueous solution A is finished, controlling the adding time of the solvent S2 to be 5-10 min, then controlling the reaction temperature to be150-160 DEG C and reaction pressure to be 4-6 atmospheric pressure, and finishing cooling after continuously reacting for 2-4 h; and 2) performing filtering and layering after the cooling of a system, and concentrating, steaming and removing the solvents to obtain a product after an organic layer is washed by water and dried by a drying agent. The method is low in raw material price, less in stepand high in yield.
Method for highly efficiently synthesizing 2-phenyl-1,3-propylene glycol
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Paragraph 0021-0026; 0027-0032; 0033-0038; 0039-0050, (2018/04/21)
The invention discloses a method for highly efficiently synthesizing 2-phenyl-1,3-propylene glycol. The method includes the following steps that firstly a silicate active agent is prepared; secondly,ethyl benzoacetate, methyl formate and diisopropyl carbodiimide are used as raw materials for condensation reaction; alpha-formyl ethyl phenylacetate is prepared; then sodium borohydride is used as ahydrogenation reductant, the prepared silicate active agent promotes a reduction reaction, and alpha-formyl ethyl phenylacetate is reduced to prepare 2-phenyl-1,3-propylene glycol. The 2-phenyl-1,3-propylene glycol prepared by the method is high in purity, high in yield, short in reaction time and low in cost.
Controlling the Conformational Energy of a Phenyl Group by Tuning the Strength of a Nonclassical CH···O Hydrogen Bond: The Case of 5-Phenyl-1,3-dioxane
Bailey, William F.,Lambert, Kyle M.,Stempel, Zachary D.,Wiberg, Kenneth B.,Mercado, Brandon Q.
, p. 12116 - 12127 (2016/12/23)
Anancomeric 5-phenyl-1,3-dioxanes provide a unique opportunity to study factors that control conformation. Whereas one might expect an axial phenyl group at C(5) of 1,3-dioxane to adopt a conformation similar to that in axial phenylcyclohexane, a series of studies including X-ray crystallography, NOE measurements, and DFT calculations demonstrate that the phenyl prefers to lie over the dioxane ring in order to position an ortho-hydrogen to participate in a stabilizing, nonclassical CH···O hydrogen bond with a ring oxygen of the dioxane. Acid-catalyzed equilibration of a series of anancomeric 2-tert-butyl-5-aryl-1,3-dioxane isomers demonstrates that remote substituents on the phenyl ring affect the conformational energy of a 5-aryl-1,3-dioxane: electron-withdrawing substituents decrease the conformational energy of the aryl group, while electron-donating substituents increase the conformational energy of the group. This effect is correlated in a very linear way to Hammett substituent parameters. In short, the strength of the CH···O hydrogen bond may be tuned in a predictable way in response to the electron-withdrawing or electron-donating ability of substituents positioned remotely on the aryl ring. This effect may be profound: a 3,5-bis-CF3 phenyl group at C(5) in 1,3-dioxane displays a pronounced preference for the axial orientation. The results are relevant to broader conformational issues involving heterocyclic systems bearing aryl substituents.
Structurally Simple Benzylidene-Type Photolabile Diol Protecting Groups
Ding, Xiong,Devalankar, Dattatray A.,Wang, Pengfei
supporting information, p. 5396 - 5399 (2016/11/06)
Two structurally simple photolabile protecting groups for releasing 1,2- and 1,3-diols have been developed. The diols can be protected in high yields and released from their corresponding acetals with high chemical efficiency.
Synthesis of oxacyclic scaffolds via dual ruthenium hydride/Bronsted acid-catalyzed isomerization/cyclization of allylic ethers
Ascic, Erhad,Ohm, Ragnhild G.,Petersen, Rico,Hansen, Mette R.,Hansen, Casper L.,Madsen, Daniel,Tanner, David,Nielsen, Thomas E.
supporting information, p. 3297 - 3300 (2014/04/03)
A ruthenium hydride/Bronsted acid-catalyzed tandem sequence is reported for the synthesis of 1,3,4,9-tetrahydropyrano[3,4-b]indoles (THPIs) and related oxacyclic scaffolds. The process was designed on the premise that readily available allylic ethers would undergo sequential isomerization, first to enol ethers (Ru catalysis), then to oxocarbenium ions (Bronsted acid catalysis) amenable to endo cyclization with tethered nucleophiles. This methodology provides not only an attractive alternative to the traditional oxa-Pictet-Spengler reaction for the synthesis of THPIs, but also convenient access to THPI congeners and other important oxacycles such as acetals.
