Dimethylamine as the key intermediate generated in situ from dimethylformamide (DMF) for the synthesis of thioamides

• Weibing Liu,
• Cui Chen and
• Hailing Liu

Beilstein J. Org. Chem. 2015, 11, 1721–1726, doi:10.3762/bjoc.11.187

• and pharmaceuticals [3][4][5][6][7][8], have attracted considerable attention for their construction and use in organic synthesis [9][10]. Many compounds containing a thioamide motif are of medicinal significance and exhibit potent biological activities. These include for example opioid activity [11

• , some of these methods have limited applications, because of harsh conditions, low yields or the need of noble-metal catalysts. Therefore the development of novel and efficient methods for the construction of the thioamide motif is highly desirable. To avoid the disadvantages of the traditional methods

• as the solvent but also as the source of dimethylamine. The present method is more practical compared to the traditional strategies and complements the classical methods for the rapid construction of thioamides. Synthesis of thioamide derivatives. Control experiments. A mechanistic rationale for the

Trifluoromethyl-substituted tetrathiafulvalenes

• Olivier Jeannin,
• Frédéric Barrière and
• Marc Fourmigué

Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73

• accordingly, several tetrathiafulvalenes bearing only one or two ester [10], nitrile [11][12][13][14], amide [7][15][16][17], thioamide [18][19][20], or halogen [5] substituents were successfully engaged in radical cation salts by electrocrystallization, with intermolecular hydrogen [21][22][23] of halogen

• –Blodgett films. The structural and electronic properties of a series of ester [15], thioester [29][30], tertiary amide and thioamide [12] TTF derivatives have been then rationalized, based on: (i) the sizeable contribution of the mesomeric form B (Scheme 1) and, (ii) an ICT from the TTF-based HOMO to the

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

• Katherine M. Byrd

Beilstein J. Org. Chem. 2015, 11, 530–562, doi:10.3762/bjoc.11.60

• other Michael acceptors. In order to improve the reactivity of amides and lactams, they have been modified in the following manner: A) placing an EWG on the nitrogen [22], B) placing an EWG on the α-carbon atom [23], C) converting the amide/lactam to a thioamide/lactam or D) activation by a Lewis acid

• thioamide method is a useful strategy. Lewis acid activation (method D) has been used commonly for the 1,4-addition of stabilized nucleophiles, but there are some exceptions. The need to activate amides and lactams adds a level of difficulty in developing asymmetric CA (ACA) reactions. Not surprisingly, a

A small azide-modified thiazole-based reporter molecule for fluorescence and mass spectrometric detection

• Stefanie Wolfram,
• Hendryk Würfel,
• Stefanie H. Habenicht,
• Christine Lembke,
• Phillipp Richter,
• Eckhard Birckner,
• Rainer Beckert and
• Georg Pohnert

Beilstein J. Org. Chem. 2014, 10, 2470–2479, doi:10.3762/bjoc.10.258

• yield (83%). The thioamide 2 bears an electron-withdrawing substituent in form of a 2-pyridyl moiety, which is important for an efficient fluorescence of the final product [6]. The α-bromoester 3 bears a bromine atom at the 4-position of the phenyl ring, which is introduced to facilitate MS detection

Amyloid-β probes: Review of structure–activity and brain-kinetics relationships

• Todd J. Eckroat,
• Abdelrahman S. Mayhoub and
• Sylvie Garneau-Tsodikova

Beilstein J. Org. Chem. 2013, 9, 1012–1044, doi:10.3762/bjoc.9.116

• amide 69, which was subsequently converted to the thioamide by using Lawesson’s reagent and cyclized to form the benzothiazole core 70 (Scheme 6B). Demethylation with BBr3 and protection of the resulting hydroxy moiety as the methoxymethyl (MOM) ether gave 71. Reduction of the nitro group to 72

A simple and efficient dual optical signaling chemodosimeter for toxic Hg(II)

• Sabir H. Mashraqui,
• Sapna A. Tripathi,
• Sushil S. Ghorpade and
• Smita R. Britto

Beilstein J. Org. Chem. 2012, 8, 1352–1357, doi:10.3762/bjoc.8.155

• ratiometric or switch-on responses even for the paramagnetic metal ions [17][18][19]. The first luminescence chemodosimeter for Hg2+ was developed by Czarnik et al. and was based on the Hg2+-mediated desulfurization of anthracene-thioamide chromophore [20][21]. Following this pioneering report, several other

Partial thioamide scan on the lipopeptaibiotic trichogin GA IV. Effects on folding and bioactivity

• Marta De Zotti,
• Barbara Biondi,
• Cristina Peggion,
• Matteo De Poli,
• Haleh Fathi,
• Simona Oancea,
• Claudio Toniolo and
• Fernando Formaggio

Beilstein J. Org. Chem. 2012, 8, 1161–1171, doi:10.3762/bjoc.8.129

• Sibiu, Romania 10.3762/bjoc.8.129 Abstract Backbone modification is a common chemical tool to control the conformation of linear peptides and to explore potentially useful effects on their biochemical and biophysical properties. The thioamide, ψ[CS-NH], group is a nearly isosteric structural mimic of

• single thioamide replacement was incorporated. Sequence positions near the N-terminus, at the center, and near the C-terminus were investigated. Our results indicate that (i) a thioamide linkage is well tolerated in the overall helical conformation of the [Leu11-OMe] lipopeptide analogue and (ii) this

• structure. A ψ[CS-NH] thioamide group is one of the closest mimics of an amide (peptide) linkage. However, it exhibits significantly different chemical and physical properties, some of which are of great potential interest to peptide chemists [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19

The Eschenmoser coupling reaction under continuous-flow conditions

• Sukhdeep Singh,
• J. Michael Köhler,
• Andreas Schober and
• G. Alexander Groß

Beilstein J. Org. Chem. 2011, 7, 1164–1172, doi:10.3762/bjoc.7.135

• is quite a valuable, metal free, carbon–carbon bond forming reaction. The necessary starting materials of type 3 can be prepared by S-alkylation of secondary thioamide or thiolactame building blocks of type 2 with α-bromoketones 1 (X = Br). The carbon–carbon coupling occurs between these building

• . Unfortunately, the S-alkylation is sometimes difficult in these cases [6]. In the case of secondary thiolactames of type 5, sulfide contraction takes place as well, but prolonged reaction time and increased reaction temperature are necessary in most cases. In contrast to this, secondary thioamide derivatives of

• blocks and secondary thiolactame and thioamide derivatives. To improve the long reaction times we investigated the Eschenmoser coupling under process intensification conditions. Therefore, reaction temperatures far beyond the solvent boiling point were applied under pressurized flow conditions for a

An overview of the key routes to the best selling 5-membered ring heterocyclic pharmaceuticals

• Marcus Baumann,
• Ian R. Baxendale,
• Steven V. Ley and
• Nikzad Nikbin

Beilstein J. Org. Chem. 2011, 7, 442–495, doi:10.3762/bjoc.7.57

• can then be converted into its thioamide analogue 301 with P2S5 in pyridine. Finally, the reaction of 301 with acetyl hydrazide (291) catalysed by acetic acid furnishes the triazole ring fused to the benzodiazepine core. Another approach [89] makes use of 1,4-benzodiazepine-N-nitrosamidine 302 as the

Synthesis and enzymatic evaluation of 2- and 4-aminothiazole- based inhibitors of neuronal nitric oxide synthase

• Graham R. Lawton,
• Haitao Ji,
• Pavel Martásek,
• Linda J. Roman and
• Richard B. Silverman

Beilstein J. Org. Chem. 2009, 5, No. 28, doi:10.3762/bjoc.5.28

• in Scheme 4. Treatment of acetonitrile with LDA followed by addition of epoxide 5 gave trans-alcohol 24 [14]. The nitrile group was converted to a thioamide using ammonium sulfide [15]. The thioamide was condensed with either ethyl bromopyruvate or an epoxide (30) [16]. Condensation produces an