- Synthesis of Diarylheptanoid Scaffolds Inspired by Calyxins i and J
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Unsaturated alcohols are prepared efficiently in two steps from o-hydroxycinnamaldehyde. The TMSOTf-mediated reaction of the γunsaturated alcohols with aldehydes creates two oxygen heterocycles and three new stereocenters in a single pot. The approach is
- Ackrill, Thomas D.,Sparkes, Hazel A.,Willis, Christine L.
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- Method for preparing olefine aldehyde by catalyzing terminal alkyne or terminal conjugated eneyne and diphosphine ligand used in method
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The invention discloses a method for preparing olefine aldehyde by catalyzing terminal alkyne or terminal conjugated eneyne and a diphosphine ligand used in the method. According to the invention, indole-substituted phosphoramidite diphosphine ligand which is stable in air and insensitive to light is synthesized by utilizing a continuous one-pot method, and the indole-substituted phosphoramidite diphosphine ligand and a rhodium catalyst are used for jointly catalyzing to successfully achieve a hydroformylation reaction of aromatic terminal alkyne and terminal conjugated eneyne under the condition of synthesis gas for the first time, so that an olefine aldehyde structure compound can be rapidly and massively prepared, and particularly, a polyolefine aldehyde structure compound which is more difficult to synthesize in the prior art can be easily prepared and synthesized, and a novel method is provided for synthesis and modification of drug molecules, intermediates and chemical products.
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Paragraph 0163; 0164
(2021/05/29)
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- Substrate-Controlled Chemo-/Enantioselective Synthesis of α-Benzylated Enals and Chiral Cyclopropane-Fused 2-Chromanone Derivatives
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Substrate-controlled cascade reactions between α,β-unsaturated aldehydes or their analogues and 2,4-dinitrobenzyl chloride in the presence of a chiral secondary amine as the catalyst and base were developed, to obtain a broad spectrum of α-benzylated enals and enantioenriched cyclopropane-fused chroman-2-one derivatives. The cyclopropane-tethered iminium ion clearly served as a key intermediate in these reactions to trigger stereochemical outcomes, one of which was supported by a control experiment. (Figure presented.).
- Byeon, Huimyoung,Ryu, Sunghyeon,Yoo, Eun Jeong,Yang, Jung Woon
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supporting information
p. 5085 - 5091
(2021/09/20)
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- Direct Access to Bridged Tetrahydroquinolines and Chromanes via an InCl3-Catalyzed Sequential Three-Component Cascade
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A sequential three-component cascade process was developed for the synthesis of bridged tetrahydroquinolines and chromanes bearing 2,6-methanobenzo[d][1,3]diazocine and 2,6-methanobenzo[g][1,3]oxazocine scaffolds, respectively, in good yields from readily
- Vachan,Karuppasamy, Muthu,Jan, Gowsia,Bhuvanesh, Nattamai,Maheswari, C. Uma,Sridharan, Vellaisamy
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p. 8062 - 8073
(2020/09/21)
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- Kinetic Resolution and Dynamic Kinetic Resolution of Chromene by Rhodium-Catalyzed Asymmetric Hydroarylation
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A highly efficient kinetic resolution and dynamic kinetic resolution of chromene is reported for the first time and they procced by a rhodium-catalyzed asymmetric hydroarylation pathway. This new approach offers versatile access to various chiral 2,3-diaryl-chromanes containing vicinal stereogenic centers, as well as the recovered chiral flavenes, in high yields with excellent ee values (s factor up to 532). Particularly noteworthy is that this strategy can be further extended to the establishment of a dynamic version of the kinetic resolution of chromene acetals and allows complete access to chiral isoflavanes and α-aryl hydrocoumarins.
- Yang, Qingjing,Wang, Yanbo,Luo, Shihui,Wang, Jun (Joelle)
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supporting information
p. 5343 - 5347
(2019/03/21)
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- Iron(III)/O2-Mediated Regioselective Oxidative Cleavage of 1-Arylbutadienes to Cinnamaldehydes
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A simple, efficient, and environmentally benevolent regioselective oxidative cleavage of 1-arylbutadienes to cinnamaldehydes mediated by iron(III) sulfate/O2 has been developed. The reaction offered good yields and excellent regioselectivity and showed good functional group tolerance (31 examples). The method is important, as few reports with limited substrate scope are available for such excellent oxidative cleavage of conjugated dienes.
- Bhowmik, Amit,Fernandes, Rodney A.
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supporting information
p. 9203 - 9207
(2019/11/14)
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- Novel cinnamaldehyde-based aspirin derivatives for the treatment of colorectal cancer
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Colorectal cancer (CRC) is a leading cause of mortality worldwide. Current treatments of CRC involve anti-cancer agents with relatively good efficacy but unselectively target both cancer and non-cancer cells. Thus, there is a need to discover and develop
- Lu, Shan,Obianom, Obinna N.,Ai, Yong
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supporting information
p. 2869 - 2874
(2018/07/25)
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- Organocatalytic asymmetric Michael/hemiacetalization/acyl transfer reaction of α-nitroketones with o-hydroxycinnamaldehydes: Synthesis of 2,4-disubstituted chromans
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An organocatalytic asymmetric cascade Michael/hemiketalization/acyl transfer reaction between o-hydroxycinnamaldehydes and α-nitroketones is developed. Prolinol TMS ether catalyst in combination with benzoic acid was found to be the most effective for this reaction which proceeds through an equilibrium of lactols to provide a single diastereomer of enantiopure 2,4-disubstituted chromans.
- Maity, Rajendra,Pan, Subhas Chandra
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supporting information
p. 1598 - 1608
(2018/03/08)
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- A Bioinspired Cascade Sequence Enables Facile Assembly of Methanodibenzo[b,f][1,5]dioxocin Flavonoid Scaffold
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A remarkable bioinspired EDDA-mediated method for the selective construction of biologically interesting and highly strained bridged methanodibenzo[b,f][1,5]dioxocin flavonoid scaffold was uncovered by starting from a variety of readily available acylphloroglucinol and 2-hydroxycinnamaldehyde substrates. This method merges a fascinating olefin isomerization/hemiacetallization/dehydration/[3 + 3]-type cycloaddition cascade reaction driven by an in situ generated chromenylium intermediate and provides a convenient and viable synthetic strategy for the efficient access of such flavonoid analogues.
- Liu, Hongxin,Wang, Yu,Guo, Xueying,Huo, Luqiong,Xu, Zhifang,Zhang, Weimin,Qiu, Shengxiang,Yang, Bao,Tan, Haibo
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supporting information
p. 546 - 549
(2018/02/10)
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- Synthesis of 2-arylbenzofuran-3-carbaldehydes: via an organocatalytic [3+2] annulation/oxidative aromatization reaction
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A novel organocatalytic [3+2] annulation/oxidative aromatization reaction of enals with 2-halophenols or β-naphthols is reported. This process enables chemo- and regioselective access to 2-arylbenzofuran-3-carbaldehydes without the use of transition metals or strong oxidants. Preliminary mechanistic studies reveal that an unprecedented, organocatalytic, direct α-arylation pathway is involved.
- Zhang, Huiwen,Ma, Chunmei,Zheng, Ziwei,Sun, Rengwei,Yu, Xinhong,Zhao, Jianhong
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supporting information
p. 4935 - 4938
(2018/05/23)
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- Bi(OTf)3-catalyzed addition of isocyanides to 2: H -chromene acetals: An efficient pathway for accessing 2-carboxamide-2 H -chromenes
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Bismuth triflate (Bi(OTf)3) is identified as an efficient catalyst for the direct addition of isocyanides to 2H-chromene acetals. The large scope of isocyanides and chromene acetals makes them suitable substrates in this catalytic system. By this synthetic strategy, a polyfunctional molecular scaffold, 2-carboxamide-2H-chromenes could be prepared efficiently in one step up to 95% yield. In addition, this efficient and practical protocol proceeded smoothly in the gram scale even when the catalytic loading was reduced to 2 mol%.
- Lyu, Longyun,Jin, Ming Yu,He, Qijie,Xie, Han,Bian, Zhaoxiang,Wang, Jun
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supporting information
p. 8088 - 8091
(2016/09/09)
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- SELECTIVE NAV1.7 INHIBITORS FOR THE TREATMENT OF DIABETES
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Provided herein are methods for treating or preventing prediabetes or diabetes, or maintaining or lowering blood or plasma glucose or maintaining or lowering blood or plasma glycated hemoglobin comprising administering to a subject in need thereof a therapeutically effective amount of a compound selectively inhibiting NaVl.7. In particular, provided herein are processes for the preparation of and intermediates used in the preparation of compounds selectively inhibiting NaV1.7, such as the compounds of Formula (I) or compounds of Formula (I').
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Paragraph 00511; 00512
(2016/06/01)
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- SODIUM CHANNEL MODULATORS FOR THE TREATMENT OF PAIN AND DIABETES
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Provided herein are sodium channel modulating Compounds, in particular NaV1.7 modulating compounds of Formula I or compounds of Formula I′: In particular, provided herein are processes for the preparation of, intermediates used in the preparation of, pharmaceutical compositions comprising, and therapeutic methods comprising administering such compounds. In particular, provided herein are compounds for the treatment of pain and diabetes.
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Paragraph 0786; 0787
(2016/06/06)
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- Expanding the scope of the Babler–Dauben oxidation: 1,3-oxidative transposition of secondary allylic alcohols
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We report the catalytic chromium-mediated oxidation of secondary allylic alcohols to give α,β-unsaturated aldehydes with exclusive (E)-stereoselectivity. This facile procedure employs catalytic PCC (5?mol?%) and periodic acid (H5IO6) as a co-oxidant. This transformation occurs specifically with aromatic substituted allyl alcohols containing both electron withdrawing and electron donating substituents as well as a range of functional groups.
- Killoran, Patrick M.,Rossington, Steven B.,Wilkinson, James A.,Hadfield, John A.
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supporting information
p. 3954 - 3957
(2016/08/09)
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- Substrate-Controlled, One-Pot Synthesis: Access to Chiral Chroman-2-one and Polycyclic Derivatives
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Based on the appropriate choice of electrophiles, one-pot, multicomponent, enantioselective domino reactions have been realized which contain a five-step sequence and provide highly efficient access to potentially bioactive chroman-2-one derivatives as a single diastereoisomer with excellent enantioselectivities and in high yields. This new strategy could significantly improve the previous protocol by directly starting from commercial 2-hydroxybenzaldehydes rather than preformed lactols, which have to be synthesized in several additional steps. (Chemical Equation Presented).
- Sun, Xue-Li,Chen, Ying-Han,Zhu, Dan-Yang,Zhang, Yan,Liu, Yan-Kai
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supporting information
p. 864 - 867
(2016/03/04)
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- Trimethylsilyl iodide mediated one-pot synthesis of 2-allyl-2H-chromenes
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A new and efficient metal-free trimethylsilyl iodide (TMSI) catalyzed one-pot synthesis of 2-allyl-2H-chromenes has been developed that takes place under mild conditions. The synthesis proceeds through a Wittig reaction by using (triphenylphosphoranylidene)acetaldehyde to form an ohydroxycinnamaldehyde derivative followed by a tandem isomerization and C-O and C-C bond-forming reactions. The procedure was carried out at room temperature in the presence of 20 mol-% of TMSI and allyltrimethylsilane in tetrahydrofuran (THF) and provided the 2-allyl-2H-chromenes in good to excellent yields.
- Padhi, Birakishore,Reddy, D. Srinivas,Mohapatra, Debendra K.
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p. 542 - 547
(2015/01/30)
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- Synthesis, cytotoxicity against human oral cancer KB cells and structure-activity relationship studies of trienone analogues of curcuminoids
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A general method for the synthesis of substituted (1E,4E,6E)-1,7- diphenylhepta-1,4,6-trien-3-ones, based on the aldol condensations of substituted 4-phenylbut-3-en-2-ones and substituted 3-phenylacrylaldehydes, was achieved. The natural trienones 4 and 5 have been synthesized by this method, together with the trienone analogues 9-20. These analogues were evaluated for their cytotoxic activity against human oral cancer KB cell line. The structure-activity relationship study has indicated that the analogues with the 1,4,6-trien-3-one function are more potent than the curcuminoid-type function. Analogues with meta-oxygen function on the aromatic rings are more potent than those in the ortho- and para-positions. Free phenolic hydroxy group is more potent than the corresponding methyl ether analogues. Among the potent trienones, compounds 11, 18 and 20 were more active than the anticancer drug ellipticine. All compounds were also evaluated against the non-cancerous Vero cells and it was found that compounds 11, 12 and 17 were much less toxic than curcumin (1); they showed high selectivity indices of 35.46, 33.46 and 31.68, respectively. These analogues are regarded as the potent trienones for anti-oral cancer study.
- Chuprajob, Thipphawan,Changtam, Chatchawan,Chokchaisiri, Ratchanaporn,Chunglok, Warangkana,Sornkaew, Nilubon,Suksamrarn, Apichart
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supporting information
p. 2839 - 2844
(2014/06/10)
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- A cascade reaction actuated by nucleophilic heterocyclic carbene catalyzed intramolecular addition of enals via homoenolate to α,β-unsaturated esters: Efficient synthesis of coumarin derivatives
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A nucleophilic heterocyclic carbene mediated intramolecular homoenolate reaction strategy for the efficient synthesis of 4-alkyl substituted coumarins is described.
- Sinu,Padmaja,Ranjini,Lakshmi, K. C. Seetha,Suresh, Eringathodi,Nair, Vijay
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supporting information
p. 68 - 71
(2013/03/28)
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- Cinnamaldehydes inhibit thioredoxin reductase and induce Nrf2: potential candidates for cancer therapy and chemoprevention
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Trans-cinnamaldehyde (CA) and its analogs 2-hydroxycinnamaldehyde and 2-benzoyloxycinnamaldehyde have been reported to possess antitumor activity. CA is also a known Nrf2 activator. In this study, a series of ortho-substituted cinnamaldehyde analogs was s
- Chew, Eng-Hui,Nagle, Amrita A.,Zhang, Yaochun,Scarmagnani, Silvia,Palaniappan, Puvithira,Bradshaw, Tracey D.,Holmgren, Arne,Westwell, Andrew D.
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experimental part
p. 98 - 111
(2011/02/22)
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- Catalytic asymmetric oxa-Michael-Michael cascade for facile construction of chiral chromans via an aminal intermediate
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An unprecedented highly enantioselective cascade oxa-Michael-Michael reaction has been developed. The simple and practical process, efficiently catalyzed by chiral diphenylprolinol TMS ether, affords a powerful access to highly functionalized syntheticall
- Zu, Liansuo,Zhang, Shilei,Xie, Hexin,Wang, Wei
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supporting information; experimental part
p. 1627 - 1630
(2009/09/06)
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- A one-pot synthesis of (E)-disubstituted alkenes by a bimetallic [Rh-Pd]-catalyzed hydrosilylation/hiyama cross-coupling sequence
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A bimetallic [Rh-Pd] catalyst was prepared by soaking into an iodide ionic gel an equimolar solution of [RhCl(PPh3)3] and Pd(OAc)2 in CH2Cl2. Its catalytic activity was evaluated by rhodium-catalyzed hydrosilylation (H), palladium-catalyzed Hiyama coupling (C), and in the one-pot hydrosilylation/Hiyama coupling sequence (H/C). It was found that the homogeneous combination [RhCl(PPh3) 3]/NaI was a superior system compared to the polyionic mono- and bimetallic rhodium catalysts in the hydrosilylation of terminal alkynes. Interestingly, the most effective catalyst in terms of stereo- and chemoselectivities was observed to be the bimetallic ionic gel [Rh-Pd] in the one-pot process leading to (E)-alkenes with good yields. The remarkable stereocontrol is ascribed to a beneficial Pd-catalyzed isomerization from the mixture of stereoisomeric vinylsilanes obtained in the initial hydrosilylation step into the more stable (E)-adduct. The [Rh-Pd] heterogeneous catalyst also showed a higher chemoselectivity than the homogeneous catalytic combination, and no detrimental formation of Sonogashira side product was observed due to an ionic-gel-mediated kinetic modulation. To illustrate its scope and limitations, the described one-pot bimetallic catalytic sequence was extended to functionalized terminal alkynes and various iodide substrates. Conjugated systems, such as hydroxycinnamaldehyde, dienes, and trienes, were synthesized in good overall yields. To avoid deactivation of the Rh species, N-heterocyclic iodides had to be added sequentially after completion of hydrosilylation.
- Thiot, Carine,Schmutz, Marc,Wagner, Alain,Mioskowski, Charles
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p. 8971 - 8978
(2008/09/17)
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- Inhibition of chitin synthases and antifungal activities by 2′-benzoyloxycinnamaldehyde from Pleuropterus ciliinervis and its derivatives
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In the course of search for potent chitin synthase inhibitors from natural resources, a novel chitin synthases inhibitor, 2′-benzoyloxycinnamaldehyde (2′-BCA) (I), was isolated from the aerial parts of Pleuropterus ciliinervis NAKAI. 2′-BCA inhibited chit
- Kang, Tae Hoon,Hwang, Eui Il,Yun, Bong Sik,Park, Ki Duk,Kwon, Byoung Mog,Shin, Chul Soo,Kim, Sung Uk
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p. 598 - 602
(2008/02/02)
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- Dearomatization of furans via [2,3]-Still-Wittig rearrangement
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Furans and benzofurans of type 1 were dearomatized via the [2,3]-Still-Wittig rearrangement. Enol ethers 2 could be isolated or isomerized to the corresponding furans 3. The substitution pattern at the homofuranylic position had a strong influence on reaction behavior. Benzofurans rearranged with the greatest efficiency, and employment of a 3-substituted benzofuran (1; R′=CH3) allowed the creation of a quaternary carbon center.
- Caruana, Patrick A.,Frontier, Alison J.
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p. 10921 - 10926
(2007/10/03)
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- One-Step Synthesis of ortho-Hydroxycinnamaldehyde
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An improved and convenient one-step procedure for the large scale synthesis of ortho-hydroxycinnamaldehyde (3a) using ortho-hydroxybenzaldehyde and vinyl acetate is described.
- Kim, Jong Han,Lee, Sangku,Kwon, Mu-Gil,Park, Yong Soo,Choi, Sung-Kyu,Kwon, Byoung-Mog
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p. 1223 - 1228
(2007/10/03)
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- Tricyclic cyanoguanidines: Synthesis, site of action and insecticidal activity of a novel class of reversible acetylcholinesterase inhibitors
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Bridged-tricyclic cyanoguanidines 1 were found to be active as insecticides. The preparation and structure-activity relationships of oxacyclic (X = O) and carbocyclic (X = CH2) analogues of 1 is described. Compounds 1 were found to inhibit acetylcholinesterase with IC50 values comparable to the organophosphate Paraoxon. Unlike organophosphates, cyanoguanidines 1 were shown to reversibly bind acetylcholinesterase. This mode of action is shared by the structurally-related natural product Huperzine A.
- Finkelstein, Bruce L.,Benner, Eric A.,Hendrixson, Maura C.,Kranis, Kevin T.,Rauh, James J.,Sethuraman, Maya R.,McCann, Stephen F.
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p. 599 - 613
(2007/10/03)
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- Double intramolecular hetero Diels-Alder reactions of α,β-unsaturated hydrazones as 1-azadienes: A new route to 2,2′-bipyridines
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Salicylaldehyde was converted into the O-propynyl- and O-butynyl α,β-unsaturated aldehydes 4 and ketones 6, subsequent reaction of which with N,N-dimethylhydrazine and alkyne homocoupling gave the 1,3-diyne bis-(hydrazones) 8, substrates for a double intramolecular hetero Diels-Alder reaction. Similar substrates 11, 15a/15c and 15b/15d were prepared from 2-(N-benzoylamino)cinnamaldehyde, hex-5-ynol and hept-6-ynol respectively. Heating the 1,3-diynyl bis(α,β-unsaturated hydrazones) 8a, 8c, 11 and 15a resulted in double intramolecular Diels-Alder reaction to give, after aromatisation by loss of dimethylamine, 2,2′-bipyridines 21-24.
- Bushby,Moody,Riddickb,Waldronc
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p. 2183 - 2193
(2007/10/03)
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- Cinnamaldehydes inhibit cyclin dependent kinase 4/cyclin D1
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A series of cinnamaldehydes was synthesized for the study of inhibitory activity against cyclin dependent kinases (CDKs). A couple of compounds selectively inhibited cyclin D1-CDK4 with an IC50 value of 7-18 μM. (C) 2000 Elsevier Science Ltd. All rights reserved.
- Jeong, Ha-Won,Kim, Mi-Ran,Son, Kwang-Hee,Young Han, Mi,Ha, Ji-Hong,Garnier, Matthieu,Meijer, Laurent,Kwon, Byoung-Mog
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p. 1819 - 1822
(2007/10/03)
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- Synthesis and biological activity of cinnamaldehydes as angiogenesis inhibitors
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A series of 2-hydroxycinnamaldehyde derivatives was synthesized for examing a structure-activity relationship for inhibition of angiogenesis. The anti-angiogenic effects of 2'-substituted cinnamaldehydes and related analogs were determined in a chick embryo chorioallantoic membrane assay system.
- Kwon, Byoung-Mog,Lee, Seung-Ho,Cho, Young-Kwon,Bok, Song-Hae,So, Seung-Ho,Youn, Mi-Ran,Chang, Soo-Ik
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p. 2473 - 2476
(2007/10/03)
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- Chemical and enzyme-catalysed syntheses of enantiopure epoxide and diol derivatives of chromene, 2,2-dimethylchromene, and 7-methoxy-2,2-dimethylchromene (precocene-1)
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Procaryotic (bacterial) dioxygenase-catalysed asymmetric dihydroxylation of chromene and 2,2-dimethylchromene to yield the (4S)-enantiomers of the corresponding cis-diols exclusively is reported. The epoxide, and derived cis- and trans-diol products from the previously reported eucaryotic (mammalian) metabolism of precocene-1 (7-methoxy-2,2-dimethylchromene), and the corresponding epoxide and diol derivatives of chromene and 2,2-dimethylchromene, have now been obtained in enantiopure form by chemical resolution of the corresponding bromohydrins using methoxy-(trifluoromethyl)phenylacetic acid (MTPA) or camphanate esters. The absolute configurations of the epoxides, cis- and trans-diols have been determined by chemical synthesis from, and stereochemical correlation with, the corresponding camphanate and MTPA esters. X-Ray crystal structure analysis has provided an unequivocal method for assignment of the absolute stereochemistry in each case.
- Boyd, Derek R.,Sharma, Narain D.,Boyle, Rosemary,Evans, Timothy A.,Malone, John F.,McCombe, Kenneth M.,Dalton, Howard,Chima, Jagdeep
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p. 1757 - 1765
(2007/10/03)
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- Biotransformation of Unsaturated Heterocyclic Rings by Pseudomonas putida to Yield cis-Diols
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New cis-diols metabolites of both aromatic and non-aromatic heterocyclic rings have been isolated from growing cultures of a mutant strain of the soil bacterium Pseudomonas putida (UV4) and stereochemically assigned; a novel heterocyclic cis-diol of benzothiophene, 2,3-dihydroxy-2,3-dihydrobenzothiophene is found to exist exclusively in the cis-configuration in water but equilibrates readily with the trans-isomer.
- Boyd, D. R.,Sharma, N. D.,Boyle, R.,McMurray, B. T.,Evans, T. A.,et al.
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- A Simple and Highly Stereoselective Route to E-α,β-Unsaturated Aldehydes
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Zinc bromide mediated reaction of α,α-bis(trimethylsilyl)-tert-butylacetaldimine (3) with a wide range of aldehydes takes place under mild conditions and affords the corresponding α,β-unsaturated aldehydes in good yields and with high E stereoselectivity (>98percent).This procedure is successfully applied to the preparation of intermediates for retinoid and natural product synthesis.
- Bellassoued, Moncef,Majidi, Assieh
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p. 2517 - 2522
(2007/10/02)
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