- Copper-Catalyzed Enantiotopic-Group-Selective Allylation of gem-Diborylalkanes
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We report a copper-catalyzed enatiotopic-group-selective allylation of gem-diborylalkanes with allyl bromides. The combination of copper(I) bromide and H8-BINOL derived phosphoramidite ligand proved to be the most effective catalytic system to provide various enantioenriched homoallylic boronate esters, containing a boron-substituted stereogenic center that is solely derived from gem-diborylalkanes, in good yields with high enantiomeric ratios under mild conditions. Experimental and theoretical studies have been conducted to elucidate the reaction mechanism, revealing how the enatiotopic-group-selective transmetalation of gem-diborylalkanes with chiral copper complex occurs to generate chiral α-borylalkyl-copper species for the first time. Additional synthetic applications to the synthesis of various chiral building blocks are also included.
- Kim, Minjae,Park, Bohyun,Shin, Minkyeong,Kim, Suyeon,Kim, Junghoon,Baik, Mu-Hyun,Cho, Seung Hwan
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p. 1069 - 1077
(2021/01/25)
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- Synthesis of Six-Membered Spiro Azacyclic Oxindole Derivatives via a One-Pot Process of Umpolung Allylation/Aza-Prins Cyclization
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An unprecedented synthetic approach involving umpolung allylation/aza-Prins cyclization of N-2,2,2-trifluoroethylisatin ketimines is described. The reactions proceed smoothly with allyl bromide in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene, H2O, and trimethylsilyl bromide; this one-pot protocol allows access to six-membered spiro azacyclic oxindole derivatives in good to excellent yields. Notably, while the general aza-Prins cyclization involves amines and aldehydes, the present synthetic strategy represents the first aza-Prins cyclization that utilizes the umpolung property of N-2,2,2-trifluoroethylisatin ketimines.
- Jang, Woo Cheol,Jung, Myeongjin,Ko, Haye Min
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p. 1510 - 1515
(2021/03/03)
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- Visible-light-promoted radical alkylation/cyclization of allylic amide with N-hydroxyphthalimide ester: Synthesis of oxazolines
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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.
- Ding, Hao,Huang, Panyi,Jin, Can,Su, Weike,Sun, Bin,Yan, Zhiyang,Zhao, Haiyun
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- Pd-Catalyzed Asymmetric Acyl-Carbamoylation of an Alkene to Construct an α-Quaternary Chiral Cycloketone
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Herein, we report the palladium-catalyzed asymmetric acyl-carbamoylation of an alkene by employing thioesters as the acyl electrophiles and t-BuNC as the carbamoyl reagent, affording an α-quaternary chiral cycloketone in synthetically useful yields with excellent enantioselectivity. The reaction proceeded via asymmetric 1,2-migratory insertions of acyl-Pd into alkenes and subsequent migratory insertion of isocyanides into C(sp3)-PdII. The product could be diversified to some valuable skeletons with retention of enantiopurity, demonstrating the synthetic utility of this protocol.
- Liu, Min,Wang, Xing,Guo, Ziqiong,Li, Hanyuan,Huang, Wei,Xu, Hui,Dai, Hui-Xiong
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supporting information
p. 6299 - 6304
(2021/08/30)
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- HETEROAROMATIC COMPOUNDS AS VANIN INHIBITORS
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The present invention encompasses compounds of the formula I which are suitable for the treatment of diseases related to Vanin, and processes for making these compounds, pharmaceutical preparations containing these compounds, and their methods of use.
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Paragraph 0308-0317
(2020/03/23)
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- 3 -trifluoromethyl -5 - aryl -1, 6 -dihydropyridazine compound and preparation method thereof (by machine translation)
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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)
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Paragraph 0048; 0050; 0054; 0056
(2020/08/25)
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- Chiral Br?nsted Acid Catalyzed Dynamic Kinetic Asymmetric Hydroamination of Racemic Allenes and Asymmetric Hydroamination of Dienes
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The first highly efficient and practical chiral Br?nsted acid catalyzed dynamic kinetic asymmetric hydroamination (DyKAH) of racemic allenes and asymmetric hydroamination of unactivated dienes with both high E/Z selectivity and enantioselectivity are described herein. The transformation proceeds through a new catalytic asymmetric model involving a highly reactive π-allylic carbocationic intermediate, generated from racemic allenes or dienes through a proton transfer mediated by an activating/directing thiourea group. This method affords expedient access to structurally diverse enantioenriched, potentially bioactive alkenyl-containing aza-heterocycles and bicyclic aza-heterocycles.
- Lin, Jin-Shun,Li, Tao-Tao,Jiao, Guan-Yuan,Gu, Qiang-Shuai,Cheng, Jiang-Tao,Lv, Ling,Liu, Xin-Yuan
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p. 7092 - 7096
(2019/04/26)
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- Highly Enantioselective Iridium-Catalyzed Hydrogenation of 2-Aryl Allyl Phthalimides
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The iridium-catalyzed asymmetric hydrogenation of 2-aryl allyl phthalimides to afford enantioenriched β-aryl-β-methyl amines is presented. Recently developed Ir-MaxPHOX catalysts are used for this enantioselective transformation. The mild reaction conditions and the feasible removal of the phthalimido group makes this catalytic method easily scalable and of great interest to afford chiral amines. The importance of this new methodology is exemplified by the formal synthesis of (R)-Lorcaserin, OTS514, and enantiomerically enriched 3-methyl indolines.
- Cabré, Albert,Romagnoli, Elia,Martínez-Balart, Pol,Verdaguer, Xavier,Riera, Antoni
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p. 9709 - 9713
(2019/11/19)
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- Rhodium-Catalyzed Enantioconvergent Isomerization of Homoallylic and Bishomoallylic Secondary Alcohols
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We present herein an unprecedented enantioselective isomerization of homoallylic and bishomoallylic secondary alcohols, catalyzed by a commercially available rhodium-complex and a base. This catalytic redox-neutral process provides an effective access to chiral ketones in high efficiency and enantioselectivity, without the use of any stoichiometric reagent or generation of any waste. For the reaction of homoallylic alcohols, this system achieved not only a stereoconvergent access to chiral ketones bearing a β-stereocenter (up to 95%, 86% ee) but also a concomitant oxidative kinetic resolution of the alcohol substrates (S > 20). In the case of bishomoallylic alcohols, an intriguing ligand-induced divergent reactivity was observed. A terminal-to-internal alkene isomerization promoted by Rh/L7 followed by redox isomerization using Rh/BINAP system produced chiral ketones bearing a γ-stereocenter with high yield and enantioselectivity. Mechanistic studies provided strong support for the redox-isomerization pathway with chain walking of the key alkyl-Rh intermediate.
- Huang, Rui-Zhi,Lau, Kai Kiat,Li, Zhaofeng,Liu, Tang-Lin,Zhao, Yu
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p. 14647 - 14654
(2018/11/06)
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- Visible-Light Photocatalytic Bicyclization of 1,7-Enynes toward Functionalized Sulfone-Containing Benzo[a]fluoren-5-ones
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A new visible-light photocatalytic arylsulfonylation and bicyclization of C(sp3)-tethered 1,7-enynes with sulfinic acids has been developed, delivering functionalized sulfone-containing benzo[a]fluoren-5-ones with generally good yields. This Eosin Y-catalyzed approach makes use of visible light as a safe and eco-friendly energy source to drive cascade cyclization reactions, resulting in continuous multiple bond-forming events including C–S and C–C bonds to efficiently construct polycyclic-linked alkyl aryl sulfones. (Figure presented.).
- Huang, Min-Hua,Zhu, Yi-Long,Hao, Wen-Juan,Wang, Ai-Fang,Wang, De-Cai,Liu, Feng,Wei, Ping,Tu, Shu-Jiang,Jiang, Bo
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p. 2229 - 2234
(2017/07/07)
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- Sulfonylative alkoxyhydroxylation of 2-arylpropenes
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One-pot three-step sulfonylative alkoxyhydroxylation of 2-arylpropenes 1 affords oxygenated sulfonylcumenes 4 in moderate yields via a sequential route: (i) NBS-mediated allylic bromination of 2-arylpropenes 1 in CH2Cl2, (ii) sodium sulfinates 2-promoted nucleophilic substitution of the resulting styryl bromides in a co-solvent of alcohol and water, and (iii) V2O5/H2O2 mediated alkoxyhydroxylation of corresponding styryl sulfones 3 in alcohol. The synthetic route provides a highly effective protocol for the 1,2,3-tricarbofunctionalization of 2-arylpropenes 1 via two carbon-oxygen and one carbon-sulfur bond formations.
- Wang, Huei-Sin,Wu, Yan-Shin,Chang, Meng-Yang
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p. 6465 - 6470
(2017/10/10)
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- Method for synthesizing 4-(4-chlorphenyl)cyclohexanone
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The invention relates to the field of organic synthesis and discloses a method for synthesizing a chemical intermediate 4-(4-chlorphenyl)cyclohexanone. The method includes the steps that firstly, 4-isopropenyl chlorobenzene is mixed with an organic solvent, N-bromo-succinimide is added for reaction for 1-6 h, solid is obtained, washed and dried after the reaction is completed, a compound 2 is obtained, a quenching reaction is carried out, extraction is conducted, an organic phase is obtained, and the compound 2 is obtained; secondly, the compound 2 and diethyl 1,3-acetonedicarboxylate are dissolved in alcohol, sodium alcoholate is added for reaction for 8-20 h, concentration is conducted after the reaction is completed, and a compound 3 is obtained; thirdly, the compound 3 is mixed with alcohol, an alkaline solution is added for a reflux reaction for 3-15 h, the product is adjusted to be alkalescent after the reaction is completed, and an organic phase is obtained, washed and dried after extraction. According to the synthesis method, raw materials are easy to obtain, reaction conditions are mild, selectivity is high, aftertreatment has good operability, the yield is high, production is easy to enlarge, and the method is more environmentally friendly.
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Paragraph 0022; 0023; 0024
(2017/08/27)
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- Organic base-catalysed solvent-tuned chemoselective carbotrifluoromethylation and oxytrifluoromethylation of unactivated alkenes
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An unprecedented and efficient organic base-catalysed highly chemoselective carbo- and oxytrifluoromethylation of unactivated alkenes with Togni's reagent was developed. The switchable chemoselectivity was tuned by simply changing the organic base catalyst and solvent. Mechanistic studies indicated that a radical cyclization pathway for carbotrifluoromethylation in DMSO and a carbocation pathway for oxytrifluoromethylation in DCE were probably involved.
- Yang, Ning-Yuan,Li, Zhong-Liang,Ye, Liu,Tan, Bin,Liu, Xin-Yuan
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p. 9052 - 9055
(2016/07/21)
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- Synthesis of 2,5-Diaryl-1,5-dienes from Allylic Bromides Using Visible-Light Photoredox Catalysis
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Visible-light photoreductive coupling of 2-arylallyl bromides in the presence of the photocatalyst Ru(bpy)3(PF6)2, a Hantzsch ester, and i-Pr2NEt gives 2,5-diaryl-1,5-dienes in high yield. This method avoids the use of stoichiometric metal reductants and is compatible with the presence of halogen, alkyl, electron-donating, and electron-withdrawing substituents on the aromatic ring.
- Pratsch, Gerald,Overman, Larry E.
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p. 11388 - 11397
(2015/12/01)
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- Novel arylalkenylpropargylamines as neuroprotective, potent, and selective monoamine oxidase B inhibitors for the treatment of Parkinson's disease
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To develop novel neuroprotective agents, a library of novel arylalkenylpropargylamines was synthesized and tested for inhibitory activities against monoamine oxidases. From this, a number of highly potent and selective monoamine oxidase B inhibitors were identified. Selected compounds were also tested for neuroprotection in in vitro studies with PC-12 cells treated with 6-OHDA and rotenone, respectively. It was observed that some of the compounds tested yielded a marked increase in survival in PC-12 cells treated with the neurotoxins. This indicates that these propargylamines are able to confer protection against the effects of the toxins and may also be considered as novel disease-modifying anti-Parkinsonian agents, which are much needed for the therapy of Parkinson's disease.
- Huleatt, Paul B.,Khoo, Mui Ling,Chua, Yi Yuan,Tan, Tiong Wei,Liew, Rou Shen,Balogh, Balázs,Deme, Ruth,G?l?ncsér, Flóra,Magyar, Kalman,Sheela, David P.,Ho, Han Kiat,Sperlágh, Beáta,Mátyus, Péter,Chai, Christina L. L.
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supporting information
p. 1400 - 1419
(2015/03/04)
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- NEW ARYLALKENYLPROPARGYLAMINE DERIVATIVES EXHIBITING NEUROPROTECTIVE ACTION FOR THE TREATMENT OF NEURODEGENERATIVE DISEASES
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The invention relates to novel arylalkenylpropargylamine derivatives of general formula (I) or enantiomers or diastereomers thereof or salts, optionally pharmaceutically acceptable salts, or solvates of any of these. The compounds can be used in treating or preventing a disease or condition in a mammal related to monoamine oxidase dysfunction, especially in neurodegenerative diseases, e.g. Parkinson's disease, Alzheimer's disease or Huntington's disease.
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Page/Page column 27; 135
(2015/06/25)
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- Catalytic enantioselective iodoaminocyclization of hydrazones
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The first catalytic enantioselective iodoaminocyclization of β,γ-unsaturated hydrazones has been developed with the help of a trans-1,2-diaminocyclohexane-derived bifunctional thiourea catalyst and allows for the direct access to δ2-pyrazolines containing a quaternary stereogenic center in high yield with good enantioselectivity (up to 95% yield and 95:5 er).
- Tripathi, Chandra Bhushan,Mukherjee, Santanu
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p. 3368 - 3371
(2014/07/08)
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- Solvent-dependent enantiodivergence in the chlorocyclization of unsaturated carbamates
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A remarkable solvent-controlled enantiodivergence is seen in the hydroquinidine 1,4-phthalazinediyl diether ((DHQD)2PHAL)-catalyzed chlorocyclization of unsaturated carbamates. Eyring plot analyses of this previously unreported reaction are used to probe and compare the R- and S-selective pathways. In the CHCl3/hexanes solvent system, the pro-R process shows a surprising increase in selectivity with increasing temperature. These studies point to a strongly solvent-dependent entropy-enthalpy balance between the pro-R and pro-S pathways. Two solvents, two enantiomers: Enantiodivergent hydroquinidine 1,4-phthalazinediyl diether ((DHQD) 2PHAL)-catalyzed chlorocyclization of unsaturated carbamates, controlled solely by the choice of solvent, yields oxazolidinones in high enantioselectivity (see scheme; DCDMH=1,3-dichloro-5,5-dimethyl hydantoin). The origin of the observed enantiodivergence is traced back to a solvent-selected entropy-enthalpy balance between pro-R and pro-S pathways that dictates the course of the reaction. Copyright
- Garzan, Atefeh,Jaganathan, Arvind,Salehi Marzijarani, Nastaran,Yousefi, Roozbeh,Whitehead, Daniel C.,Jackson, James E.,Borhan, Babak
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p. 9015 - 9021
(2013/07/26)
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- Catalytic enantioselective iodoetherification of oximes
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Organocatalysis: The first catalytic enantioselective iodoetherification of oximes is developed using commercially available N-iodosuccinimide. In the presence of a dihydrocinchonidine-derived thiourea (10 mol %), β,γ-unsaturated oximes undergo facile iodoetherification to produce Δ2-isoxazolines containing a quaternary stereogenic center generally in high yield with good to excellent enantioselectivity. Copyright
- Tripathi, Chandra Bhushan,Mukherjee, Santanu
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p. 8450 - 8453
(2013/09/02)
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- CYANOGUANIDINE-SUBSTITUTED PYRAZOLINES
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The invention relates to the field of blood coagulation and, in particular, to the use of cyanoguanidine-substituted pyrazolines as medicaments, novel cyanoguanidine-substituted pyrazolines of formula (1) and to methods for the production thereof, in addition to the use thereof for producing medicaments for treating and/or for the prophylaxis of illnesses, in particular cardiovascular diseases, preferably thromboembolic diseases.
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Page/Page column 37-38
(2008/06/13)
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- AZETIDINE-SUBSTITUTED PYRAZOLINES AS PAR-1 ANTAGONISTS
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The invention relates to blood clotting, and especially to the use of azetidine-substituted pyrazolines as medicaments, novel azetidine-substituted pyrazolines, methods for the production thereof, and the use of the same for producing medicaments for the treatment and/or prophylaxis of diseases, especially cardiovascular diseases, preferably thromboembolic diseases.
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Page/Page column 33
(2008/06/13)
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- Design, synthesis, and biological evaluation of semicarbazide-sensitive amine oxidase (SSAO) inhibitors with anti-inflammatory activity
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In an attempt to examine the effect of inhibition of semicarbazide- sensitive amine oxidase (SSAO; EC 1.4.3.6, also known as VAP-1) as a novel anti-inflammatory target, the structure/mechanism based design and synthesis of a series of novel hydrazino-cont
- Wang, Eric Y.,Gao, Hongfeng,Salter-Cid, Luisa,Zhang, Jun,Huang, Li,Podar, Erika M.,Miller, Andrew,Zhao, Jingjing,O'Rourke, Anne,Linnik, Matthew D.
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p. 2166 - 2173
(2007/10/03)
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- Characterization of a series of 3-amino-2-phenylpropene derivatives as novel bovine chromaffin vesicular monoamine transporter inhibitors
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A series of 3-amino-2-phenylpropene (APP) derivatives have been synthesized and characterized as novel competitive inhibitors, with Ki values in the μM range, for the bovine chromaffin granule membrane monoamine transporter(s) (bVMAT). Although, these inhibitors are structurally similar to the bVMAT substrate tyramine, none of them were measurably transported into the granule. Structure - activity studies have revealed that, while the 3′- or 4′-OH groups on the aromatic ring enhance the inhibition potency, Me or OMe groups in these positions reduce the inhibition potency. Halogen substitution on the 4′-position of the aromatic ring causes gradual increase of the inhibition potency parallel to the electron donor ability of the halogen. Substituents on the NH2 as well as on the 3-position of the alkyl chain reduce the inhibition potency. Comparative structure - activity analyses of APP derivatives with tyramine and the neurotoxin 1-methyl-4-phenylpyridinium suggest that the flexibility of the side chain and the relative orientation of the NH2 group may be critical for the efficient transport of the substrate through the bVMAT. Comparable bVMAT affinities of these inhibitors to that of DA and other pharmacologically active amines suggest that they are suitable for the structure activity and mechanistic studies of monoamine transporters and may also be useful in modeling the mechanism of action of amphetamine-related derivatives.
- Perera, Rohan P.,Wimalasena, D. Shyamali,Wimalasena, Kandatege
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p. 2599 - 2605
(2007/10/03)
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- An intriguing effect of Yb(OTf)3-TMSCl in the halogenation of 1,1-disubstituted alkenes by NXS: Selective synthesis of allyl halides
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A novel protocol to effect the efficient selective halogenation of 1,1-disubstituted alkenes with NXS catalyzed by Yb(OTf)3-TMSCl, which affords the corresponding allyl halides in high yield, including allyl bromide, chloride, iodide and fluori
- Yamanaka, Masamichi,Arisawa, Mitsuhiro,Nishida, Atsushi,Nakagawa, Masako
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p. 2403 - 2406
(2007/10/03)
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- Arthropodicidal pyrazolines, pyrazolidines and hydrazines
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Arthropodicidal pyrazoline, pyrazolidine and hydrazine compounds, including all their geometric and stereoisomers, agriculturally suitable salts thereof and compositions containing them; and a method for controlling arthropods employing said compounds which are: STR1 wherein Q, X, X1, Y and G are as defined in the text.
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- Potential GabaB Receptor Antagonists. V. The Application of Radical Additions to Styrenes to Produce 2-Hydroxysaclofen
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3-Amino-2-(4-chlorophenyl)-2-hydroxypropanesulfonic acid (2-hydroxysaclofen), and its 2-phenyl analogue have been synthesized by three methods.Two involve the oxygen-catalysed free radical addition of bisulfite to the corresponding 3-aminopropene or 3-pht
- Abbenante, Giovanni,Prager, Rolf H.
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p. 1791 - 1800
(2007/10/02)
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