- Anodic Oxidation of Aminotetrazoles: A Mild and Safe Route to Isocyanides
-
A new electrochemical method for the preparation of isocyanides from easily accessible aminotetrazole derivatives has been developed, which tolerates an unprecedented range of functional groups. The use of chemical, rather than electrochemical, oxidation to afford isocyanides was also demonstrated, which provides access to these compounds for those without electrosynthesis equipment. The practicality of scale-up using flow electrochemistry has been demonstrated, in addition to the possibility of using electrochemically generated isocyanides in further reactions.
- Leech, Matthew C.,Petti, Alessia,Tanbouza, Nour,Mastrodonato, Andrea,Goodall, Iain C. A.,Ollevier, Thierry,Dobbs, Adrian P.,Lam, Kevin
-
supporting information
p. 9371 - 9375
(2021/12/09)
-
- (o-Phenylenediamino)borylstannanes: Efficient Reagents for Borylation of Various Alkyl Radical Precursors
-
(o-Phenylenediamino)borylstannanes were newly synthesized to achieve radical boryl substitutions of a variety of alkyl radical precursors. Dehalogenative, deaminative, decharcogenative, and decarboxylative borylations proceeded in the presence of a radica
- Suzuki, Kensuke,Nishimoto, Yoshihiro,Yasuda, Makoto
-
supporting information
p. 3968 - 3973
(2020/12/30)
-
- Synthesis of isocyanides by reacting primary amines with difluorocarbene
-
A general, convenient, and friendly route for preparing a versatile building block of isocyanides from primary amines is developed. Difluorocarbene, generated in situ from decarboxylation of chlorodifluoroacetate, reacts efficiently with primary amines to produce isocyanides. Various primary amines are well tolerated, including aryl, heteroaryl, benzyl, and alkyl amines, as well as amine residues in amino acids and peptides. Late-stage functionalization of biologically active amines is demonstrated, showing its practical capacity in drug design and peptide modification.
- Si, Yi-Xin,Zhu, Peng-Fei,Zhang, Song-Lin
-
supporting information
p. 9086 - 9090
(2020/11/30)
-
- [3+2] Anionic Cycloaddition of Isocyanides to Acyclic Enamines and Enaminones: A New, Simple, and Convenient Method for the Synthesis of 2,4-Disubstituted Pyrroles
-
We herein demonstrate a new approach for the synthesis of 2,4-disubstituted pyrroles by [3+2] cycloaddition reaction of isocyanides to the activated double bond of various enamines and enaminones. This process paved the way for the synthesis a series of 2,4-disubstituted pyrroles, which are known to be intermediates in the synthesis of biologically active compounds, in good to excellent yields from simple and commercially available starting materials. The process is carried out efficiently using a strong base, tBuOK, at low temperatures (0 °C). The described method is simple, proceeds in one step, does not require additional catalysts and hence, has a wide scope.
- Bakulev, Vasiliy A.,Efimov, Ilya V.,Luque, Rafael,Matveeva, Maria D.,Voskressensky, Leonid G.
-
supporting information
(2020/02/27)
-
- Nonacidic Farnesoid X Receptor Modulators
-
As a cellular bile acid sensor, farnesoid X receptor (FXR) participates in regulation of bile acid, lipid and glucose homeostasis, and liver protection. Clinical results have validated FXR as therapeutic target in hepatic and metabolic diseases. To date, potent FXR agonists share a negatively ionizable function that might compromise their pharmacokinetic distribution and behavior. Here we report the development and characterization of a high-affinity FXR modulator not comprising an acidic residue.
- Flesch, Daniel,Cheung, Sun-Yee,Schmidt, Jurema,Gabler, Matthias,Heitel, Pascal,Kramer, Jan,Kaiser, Astrid,Hartmann, Markus,Lindner, Mara,Lüddens-D?mgen, Kerstin,Heering, Jan,Lamers, Christina,Lüddens, Hartmut,Wurglics, Mario,Proschak, Ewgenij,Schubert-Zsilavecz, Manfred,Merk, Daniel
-
supporting information
p. 7199 - 7205
(2017/09/07)
-
- Enantioselective Synthesis of Quaternary Δ4- and Δ5-Dehydroprolines Based on a Two-Step Formal [3+2] Cycloaddition of α-Aryl and α-Alkyl Isocyano(thio)acetates with Vinyl Ketones
-
A divergent synthesis of optically active quaternary Δ4- and Δ5-dehydro prolines is developed based on the first catalytic enantioselective conjugate addition of α-substituted isocyano(thio)acetates to vinyl ketones that is general for both α-aryl and α-alkyl isocyano(thio)acetates. The new tetrasubstituted C?N stereocenter is formed without the need of any metal salt due to a bifunctional tertiary amine/squaramide catalyst, featuring a bulky polyaryl sidearm and an unusually short squaramide diamide H???H interatomic distance in the solid state.
- Odriozola, Amaiur,Oiarbide, Mikel,Palomo, Claudio
-
supporting information
p. 12758 - 12762
(2017/09/25)
-
- Synthesis of isocyanides through dehydration of formamides using XtalFluor-E
-
The formation of isocyanides from formamides using XtalFluor-E, [Et2NSF2]BF4, is presented. A wide range of formamides can be used to produce the corresponding isocyanides in up to 99% yield. In a number of cases, the crude products showed good purity (generally >80% by NMR) allowing to be used directly in multi-component reactions.
- Keita, Massaba,Vandamme, Mathilde,Mahé, Olivier,Paquin, Jean-Fran?ois
-
supporting information
p. 461 - 464
(2015/03/05)
-
- Synthesis of imidazo[1,2-a]pyridines in a sequential one-pot Groebke-Blackburn modification using 2-aminopyridines, aldehydes and amines
-
Herein we present a novel synthetic procedure for the synthesis of imidazo[1,2-a]pyridines in a modified Groebke-Blackburn fashion. In a sequential three-step one-pot protocol the commercially hardly available isocyanide-component is formed in situ using standard reagents. Cyclization to the desired products can be afforded in the same reaction mixture. The absent need of isolation of the isocyanide in this protocol eases its handling considerably and workup is only needed to finally furnish the imidazo[1,2-a]pyridines via coloumn chromatography. This protocol is a convenient way to more diverse libraries of imidazo[1,2-a]pyridines extending the functionality of the Groebke-Blackburn synthesis.
- Flesch,Schubert-Zsilavecz
-
p. 507 - 510
(2015/09/15)
-
- Novel ultrasound-promoted parallel synthesis of trifluoroatrolactamide library via a one-pot passerini/hydrolysis reaction sequence and their fungicidal activities
-
An ultrasound-promoted one-pot Passerini/hydrolysis reaction sequence has been developed for the synthesis of trifluoroatrolactamide derivatives using a diverse range of trifluoroacetophenones and isonitriles in acetic acid. Parallel synthesis in a centrifuge tube using a noncontact ultrasonic cell crusher was used in this study as an efficient method for the rapid generation of combinatorial trifluoroatrolactamide libraries, and subsequent biochemical evaluation of the resulting compounds indicated that they possessed excellent broad-spectrum fungicidal activities. N-(4-chlorophenyl)-2-(4-ethylphenyl)-3,3, 3-trifluoro-2-hydroxypropanamide and N-(4-chlorophenyl)-3,3,3-trifluoro-2- hydroxy-2-(4-methoxyphenyl)propanamide, in particular, showed significant fungicidal activities against all of the fungal species tested in the current study.
- Yu, Shu-Jing,Zhu, Cong,Bian, Qiang,Cui, Can,Du, Xiu-Jiang,Li, Zheng-Ming,Zhao, Wei-Guang
-
supporting information
p. 17 - 23
(2014/02/14)
-
- A general simple methodology for synthesis of isonitriles using benzene-1,3-disulfonyl dichloride
-
Isonitrile derivatives have been synthesized in good to high yields by dehydration of aliphatic and aromatic formamides in the presence of benzene-1,3-disulfonyl dichloride as easy and efficient reagent.
- Ghorbani-Vaghei, Ramin,Amiri, Mostafa,Veisi, Hojat
-
-
- Catalytic enantioselective Michael addition of α-aryl-α- isocyanoacetates to vinyl selenone: Synthesis of α,α-disubstituted α-amino acids and (+)- and (-)-trigonoliimine A
-
Be like Mike: The title reaction in the presence of the catalyst 1 afforded Michael adducts in excellent yields and enantioselectivities. The adducts were readily converted into α,α′-disubstituted α-amino acids. The enantioselective total synthesis of bot
- Buyck, Thomas,Wang, Qian,Zhu, Jieping
-
supporting information
p. 12714 - 12718
(2013/12/04)
-
- Isocyanide-based multicomponent reaction 'without' isocyanides
-
We present here a one-pot, four-component sequence that affords Ugi-type adducts starting from simple benzyl or allyl bromides. The isocyanides are prepared in situ under alkylation of silver cyanide salts and the resulting mixture is directly used in a U
- El Kaim, Laurent,Grimaud, Laurence,Schiltz, Aurélie
-
experimental part
p. 1401 - 1404
(2009/10/19)
-
- One-pot synthesis of oxazoles using isocyanide surrogates
-
We wish to present herein a simple one-pot synthesis of 2,5-disubstituted oxazoles, starting from benzyl halides and acyl chlorides. The in situ formation of isocyanides, followed by the addition of an acyl chloride in the presence of a base leads to the
- Kaim, Laurent El,Grimaud, Laurence,Schiltz, Aurélie
-
experimental part
p. 5235 - 5237
(2009/12/06)
-
- Microwave-assisted synthesis of isonitriles: A general simple methodology
-
(Chemical Equation Presented) A facile conversion of formamides to isonitriles under very mild conditions and microwave irradiation is described. This simple and efficient method has been applied for the synthesis of both aliphatic and aromatic isonitriles in high yields.
- Porcheddu, Andrea,Giacomelli, Giampaolo,Salaris, Margherita
-
p. 2361 - 2363
(2007/10/03)
-
- An improved approach for the synthesis of α,α-dialkyl glycine derivatives by the Ugi-Passerini reaction
-
A general and simple strategy for routine peptide synthesis with α,α-dialkyl glycines taking advantage of the four-component Ugi-Passerini reaction is presented. The isonitrile required for the reaction can be relatively simple and its selection based on cost, as the group it generates is easily removed under acidic conditions; in addition, this removal is not visibly affected by the bulkiness of the α-alkyl groups. Being a good leaving group from the N-terminal amino group of the amino acid, 4-methoxybenzyl was the choice for the amine component of the reaction. The method is illustrated with the synthesis of a series of acyl derivatives of several α,α-dialkyl glycines. The preparation of the latter compounds is also reported.
- Costa, Susana P.G.,Maia, Hernani L.S.,Pereira-Lima, Silvia M.M.A.
-
p. 1475 - 1479
(2007/10/03)
-
- 1,3-Diphenylpropan-1,3-diamines IX. Reaction of α-Chlorooxime Ethers with α-Lithiobenzylamines
-
The carbanions of the benzylamine derivatives 1-4 have been reacted with α-chlorooxime ether 5 in order to get precursors of 1,3-diphenylpropane-1,3-diamines.Isonitrile 1 afforded the expected result, whereas lithiated benzamide 2 underwent oxidative dimerization and transmetallated chlorooxime derivative 5.Isoxazolidine 3 gave the condensation product 21 as a mixture of diastereomers; treatment of imine 4 led to the desired amine-oxime 15 in low yield. - Keywords: 1,3-Diphenylpropane-1,3-diamines; Benzylamine carbanions; α-Chloroacetophenone-oxime O-methyl ether
- Kaiser, A.,Wiegrebe, W.
-
p. 763 - 774
(2007/10/03)
-
- 3-Phenyl-substituted imidazo[1,5-a]quinoxalin-4-ones and imidazo[1,5- a]quinoxaline ureas that have high affinity at the GABA(A)/benzodiazepine receptor complex
-
A series of imidazo[1,5-a]quinoxalin-4-ones and imidazo[1,5- a]quinoxaline ureas containing substituted phenyl groups at the 3-position was developed. Compounds within the imidazo-[1,5-a]quinoxaline urea series had high affinity for the GABA(A)/benzodiaze
- Jacobsen, E. Jon,Stelzer, Lindsay S.,Belonga, Kenneth L.,Carter, Donald B.,Im, Wha Bin,Sethy, Vimala H.,Tang, Andrew H.,Von Voigtlander, Philip F.,Petke, James D.
-
p. 3820 - 3836
(2007/10/03)
-
- Novel hexakis(areneisonitrile)technetium(I) complexes as radioligands targeted to the multidrug resistance P-glycoprotein
-
Transport substrates and modulators of the human multidrug resistance (MDR1) P-glycoprotein (Pgp) are generally lipophilic cationic compounds, many with substituted aryl moieties. We sought to synthesize aromatic technetium isonitrile complexes to enable
- Herman,Sharma,Kronauge,Barbarics,Herman,Piwnica- Worms
-
p. 2955 - 2963
(2007/10/02)
-