- On the development of a nucleophilic methylthiolation methodology
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Methylthiolation reactions are usually explored to access organosulfur compounds using methanethiol, an extremely flammable and toxic compound. Herein, methylthiomethyl esters were successfully applied as novel methylthiolation reagents in a low cost, transition-metal-free methodology. These reagents allowed the methylthiolation of a wide scope of chalcones, acyl ester derivatives and Morita-Baylis-Hillman acetates with good group tolerance, affording the methylthiolated products in moderate to excellent yields. The reaction mechanism was investigated through several control experiments, as well as by theoretical calculations employing Density Functional Theory. The results strongly support that a sulfurane and a sulfonium ylide appear as key intermediates and that a Pummerer type rearrangement is also crucial for the formation of this novel reagent. Furthermore, the methylthiolation mechanism is likely to proceed through the nucleophilic attack of the reagent, followed by an entropically favoured step involving the acetate attack to the positively charged species, then releasing the product. This journal is
- Carvalho, Bernardo Basbaum Portinho De Puga,Amaral, Adriane Antonia Pereira,De Castro, Pedro P?ssa,Ferreira, Fernanda Cerqueira Moreira,Horta, Bruno Araújo Cautiero,Amarante, Giovanni Wilson
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p. 5420 - 5426
(2020/08/03)
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- Silver/palladium relay catalyzed 1,3-dipole annulation/allylation reactions to access fully substituted allyl imidazolidines
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A silver/palladium relay catalyzed 1,3-dipole annulation/allylation reaction of iminoesters and Baylis-Hillman acetates for the construction of fully substituted allyl imidazolidines is reported. The reaction of both iminoesters and Baylis-Hillman acetate
- Han, Ruiping,Ding, Yue,Jin, Xueke,Li, Er-Qing
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supporting information
p. 646 - 649
(2020/02/11)
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- Design, synthesis, biological evaluation and cocrystal structures with tubulin of chiral β-lactam bridged combretastatin A-4 analogues as potent antitumor agents
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A diverse of chiral β-lactam bridged analogues of combretastatin A-4 (CA-4), 3-substituted 1,4-diaryl-2-azetidinones, were asymmetrically synthesized and biologically evaluated, leading to identify a number of potent anti-proliferative compounds represent
- Zhou, Pengfei,Liang, Yuru,Zhang, Hao,Jiang, Hao,Feng, Kechang,Xu, Pan,Wang, Jie,Wang, Xiaoming,Ding, Kuiling,Luo, Cheng,Liu, Mingming,Wang, Yang
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p. 817 - 842
(2018/01/10)
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- Fe(III)-Catalyzed Hydroallylation of Unactivated Alkenes with Morita-Baylis-Hillman Adducts
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An Fe(III)-catalyzed hydroallylation of unactivated alkenes with Morita-Baylis-Hillman adducts via an Fe-catalyzed process is described. A variety of alkenes, including mono-, di-, and trisubstituted alkenes, could all smoothly convert to structural diver
- Qi, Jifeng,Zheng, Jing,Cui, Sunliang
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supporting information
p. 1355 - 1358
(2018/03/09)
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- 2-Azetidinones: Synthesis and biological evaluation as potential anti-breast cancer agents
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A series of twenty-five 2-azitidinone (β-lactam) derivatives were synthesized and evaluated for anti-cancer properties against breast cancer, MCF-7 and MDA-MB-231. These β-lactam derivatives depicted significant cytotoxicity in cancer cell lines but not i
- Geesala, Ramasatyaveni,Gangasani, Jagadeesh Kumar,Budde, Mahender,Balasubramanian, Sridhar,Vaidya, Jayathirtha Rao,Das, Amitava
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p. 544 - 558
(2016/09/09)
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- One-pot synthesis of allyl thioacetate from benzaldehydes and activated alkenes using the Morita-Baylis-Hillman reaction as a key step
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An efficient, regioselective and steresoselecitive one-pot protocol for the synthesis of (Z)-S-2-alkoxycarbonyl-3-acylallyl ethanethioates and (E)-S-2-cyano-3-acylallyl ethanethioates from benzaldehydes and activated alkenes (methyl acrylate and acrylonit
- Yang, Hae-Won,Choi, Ji-Su,Lee, Sang-Jin,Yoo, Byung-Woo,Yoon, Cheol Min
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p. 134 - 140
(2016/03/30)
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- Probing the mechanism of allylic substitution of morita-baylis- Hillman acetates (MBHAS) by using the silyl phosphonite paradigm: Scope and applications of a versatile transformation
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A P-C bond-forming reaction between silyl phosphonites and Morita-Baylis-Hillman acetates (MBHAs) is explored as a general alternative towards medicinally relevant ?2;-carboxyphosphinic structural motifs. Conversion rates of diversely substituted MBHAs to phosphinic acids 9 or 14that were recorded by using 31P NMR spectroscopy revealed unexpected reactivity differences between ester and nitrile derivatives. These kinetic profiles and DFT calculations support a mechanistic scenario in which observed differences can be explained from the "lateness" of transition states. In addition, we provide experimental evidence suggesting that enolates due to initial P-Michael addition are not formed. Based on the proposed mechanistic scenario in conjunction with DFT calculations, an interpretation of the E/Z stereoselectivity differences between ester and nitriles is proposed. Synthetic opportunities stemming from this transformation are presented, which deal with the preparation of several synthetically capricious phosphinic building blocks, whose access through the classical P-Michael synthetic route is not straightforward.
- Kalyva, Maria,Zografos, Alexandros L.,Kapourani, Era,Giambazolias, Evaggelos,Devel, Laurent,Papakyriakou, Athanasios,Dive, Vincent,Lazarou, Yannis G.,Georgiadis, Dimitris
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supporting information
p. 3278 - 3289
(2015/03/05)
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- PYRIDOPYRIMIDINE BASED DERIVATIVES AS POTENTIAL PHOSPHODIESTERASE 3 (PDE3) INHIBITORS AND A PROCESS FOR THE PREPARATION THEREOF
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The present invention provides compounds of formula 1 as potential phosphodiesterase3 (PDE3) inhibitory agents and a process for the preparation thereof. The derivatives of formula 1 can be employed as therapeutics in human and veterinary medicine, where
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Paragraph 0082; 0103; 0104; 0106
(2014/08/19)
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- INDOLIZINONE BASED DERIVATIVES AS POTENTIAL PHOSPHODIESTERASE 3 (PDE3) INHIBITORS AND A PROCESS FOR THE PREPARATION THEREOF
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The present invention provides compounds of general formula A useful as potential phosphodiesterase3 (PDE3) inhibitory agents and a process for the preparation thereof. The derivatives of formula A can be employed as therapeutics in human and veterinary medicine, where they can be used, for example, for the treatment and prophylaxis of the following diseases: heart failure, dilated cardiomyopathy, platelet inhibitors, cancer and obstructive pulmonary diseases.
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Paragraph 0077
(2014/10/16)
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- DMAP-catalyzed [3 + 2] and [4 + 2] cycloaddition reactions between [60]fullerene and unmodified Morita-Baylis-Hillman adducts in the presence of Ac2O
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One-step DMAP-catalyzed [3 + 2] and [4 + 2] cycloaddition reactions between C60 and unmodified Morita-Baylis-Hillman adducts in the presence of Ac2O have been developed for the easy preparation of cyclopentene- and cyclohexene-fused
- Yang, Hai-Tao,Ren, Wen-Long,Miao, Chun-Bao,Dong, Chun-Ping,Yang, Yang,Xi, Hai-Tao,Meng, Qi,Jiang, Yan,Sun, Xiao-Qiang
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p. 1163 - 1170
(2013/04/10)
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- Synthesis and evaluation of novel 2-pyridone derivatives as inhibitors of phosphodiesterase3 (PDE3): A target for heart failure and platelet aggregation
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Twenty-six 2-pyridone derivatives (8a-8z), which are structurally analogous to amrinone and milrinone two important cardiotonic drugs, are synthesized and characterized. The synthesis of 2-pyridone derivatives involves addition, followed by cyclization be
- Ravinder, Mettu,Mahendar, Budde,Mattapally, Saidulu,Hamsini, Kommi Venkata,Reddy, Thatikonda Narendar,Rohit, Chilappa,Srinivas, Kolupula,Banerjee, Sanjay Kumar,Rao, Vaidya Jayathirtha
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p. 6010 - 6015
(2012/11/07)
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- Iodine-mediated intramolecular electrophilic aromatic cyclization in allylamines: A general route to synthesis of quinolines, pyrazolo[4,3-b] pyridines, and thieno[3,2-b]pyridines
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An unprecedented synthesis of aromatic ring annulated pyridines from suitably substituted primary allylamines via intramolecular electrophilic aromatic cyclization mediated by molecular iodine under mild conditions is described.
- Batchu, Harikrishna,Bhattacharyya, Soumya,Batra, Sanjay
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supporting information
p. 6330 - 6333
(2013/02/23)
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- Aromatic spiroketal bisphosphine ligands: Palladium-catalyzed asymmetric allylic amination of racemic Morita-Baylis-Hillman adducts
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Showing a backbone: The spiroketal backbone of the bis(phosphine) ligand 1 led to good regio- and enantioselectivity in the palladium-catalyzed asymmetric allylic amination of racemic Morita-Baylis-Hillman adducts with aromatic amines. The methodology provides a facile and efficient synthesis of precursors for optically active β-lactam derivatives, including the cholesterol drug Ezetimibe.
- Wang, Xiaoming,Meng, Fanye,Wang, Yan,Han, Zhaobin,Chen, Yong-Jun,Liu, Li,Wang, Zheng,Ding, Kuiling
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supporting information
p. 9276 - 9282
(2012/10/29)
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- Tailored α-methylene-γ-butyrolactones and their effects on growth suppression in pancreatic carcinoma cells
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A selected series of racemic α-methylene-γ-butyrolactones (AMGBL) were synthesized via allylboration and screened against three human pancreatic cancer cell lines (Panc-1, MIA PaCa-2, and BxPC-3). This systematic study established a discernible relationsh
- Ramachandran, P. Veeraraghavan,Pratihar, Debarshi,Nair, Hari Narayanan G.,Walters, Matthew,Smith, Sadie,Yip-Schneider, Michele T.,Wu, Huangbing,Schmidt, C. Max
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supporting information; scheme or table
p. 6620 - 6623
(2010/12/19)
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- QUINOLINE, NAPHTHALENE AND CONFORMATIONALLY CONSTRAINED QUINOLINE OR NAPHTHALENE DERIVATES AS ANTI-MYCOBACTERIAL AGENTS
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The invention relates to a compound of general formula I, II, III, IV V VI, VII, VIII, IX, X or a tautomer and the stereochemically isomeric forms thereof or pharmaceutically acceptable salts thereof, a N-oxide form thereof or a pro-drug thereof. The compound is usable as a medicament for the treatment of mycobacterial disease
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Page/Page column 19
(2009/08/16)
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- Trifluoroacetic acid: a more effective and efficient reagent for the synthesis of 3-arylmethylene-3,4-dihydro-1H-quinolin-2-ones and 3-arylmethyl-2-amino-quinolines from Baylis-Hillman derivatives via Claisen rearrangement
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Trifluoroacetic acid has been discovered to be a highly effective and efficient reagent for the tandem Claisen rearrangement and cyclization reaction to yield 3-arylmethylene-3,4-dihydro-1H-quinolin-2-ones from compounds obtained from the SN2 r
- Pathak, Richa,Madapa, Sudharshan,Batra, Sanjay
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p. 451 - 460
(2007/10/03)
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- Sodium hydride mediated cascade reaction towards the synthesis of 1,5-disubstituted uracil from cyanamides derived from Baylis-Hillman adducts
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The substituted cyanamides generated from Baylis-Hillman adducts afford 1,5-disubstituted uracils via a sodium hydride induced cascade reaction involving sequential intramolecular attack of the hydroxy group on the nitrile group, cyclization of the result
- Nag,Yadav,Maulik,Batra
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p. 911 - 917
(2007/12/27)
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- Identification of 6-substituted 4-arylsulfonyl-1,4-diazepane-2,5-diones as a novel scaffold for human chymase inhibitors
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A novel series of 6-substituted 4-sulfonyl-1,4-diazepane-2,5-diones were designed, synthesized and evaluated as human chymase inhibitors. Structure-activity relationship studies led to the identification of a potent inhibitor, (6S)-6-(5-chloro-2-methoxybe
- Tanaka, Taisaku,Muto, Tsuyoshi,Maruoka, Hiroshi,Imajo, Seiichi,Fukami, Harukazu,Tomimori, Yoshiaki,Fukuda, Yoshiaki,Nakatsuka, Takashi
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p. 3431 - 3434
(2008/02/10)
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- Enantioselective allylic substitution of Morita-Baylis-Hillman adducts catalyzed by planar chiral [2.2]paracyclophane monophosphines
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Planar chiral [2,2]cyclophane monophosphines are efficient catalyst in the reaction of Morita-Baylis-Hillman adducts with phthalimide. The corresponding allylic substituted products were afforded in high yields and in good to moderate ee.
- Zhang, Tang-Zhi,Dai, Li-Xin,Hou, Xue-Long
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p. 1990 - 1994
(2008/02/13)
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- Preparation of N-protected allylic amines and α-methylene-β- amino acids from vinylalumination/Baylis-Hillman products via tandem S N2′ substitution-Overman rearrangement
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SN2′ reaction on the acetates obtained from vinylalumination or Baylis-Hillman products, followed by in situ reduction afforded allylic alcohols. Upon conversion to trichloroacetimidates and [3,3]-sigmatropic rearrangement, the corresponding N-protected β-substituted allylic amines were obtained in good yields. Utilization of hydroxy group as the nucleophile furnished allylic hydroxy esters, which were converted to protected α-methylene-β-amino acids via Overman rearrangement.
- Ramachandran, P. Veeraraghavan,Burghardt, Thomas E.,Reddy, M. Venkat Ram
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p. 2121 - 2124
(2007/10/03)
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- Esters α-methyleniques par substitution d'ethers et d'acetates derives de l'α-(hydroxymethyl)acrylate d'ethyle
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α-(Methylene)alkanoic esters are prepared in high yields by substitution of α-(acetoxymethyl)acrylates using Grignard reagents in the presence of a catalytic amount of copper(I) salt.This reaction can be applied to lithium enolates of esters and ketones a
- Amri, Hassen,Rambaud, Monique,Villieras, Jean
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