- Direct conversion of aldehydes to acyl azides using tert-butyl hypochlorite
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A general method, for the direct conversion of aldehydes to acyl azides using tert-butyl hypochlorite and sodium azide is described. The method is simple and occurs under mild conditions.
- Arote, Nitin D.,Akamanchi, Krishnacharya G.
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- Boron-Containing Nucleosides. 1. Synthesis of the Novel Heterocycle 2-Benzyl-1,4-dihydro-1-hydroxythieno[3,2-c7] [1,5,2]diazaborin-3(2H)-one: A Thieno-fused 4-Borauracil
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The synthesis of the novel boron-containing nucleobase 2-benzy]-1,4-dihydro-l-hydroxythieno[3,2-c]-[1,5,2]diazaborin-3(2H)-one (8), a thieno-fused 4-borauracil, is described. Compound 8 was prepared in three steps starting from 2-thiophenecarbonyl chlorid
- Graham, Steven M.,Ohrtman, Loralee M.
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- Copper-mediated amidation of alkenylzirconocenes with acyl azides: Formation of enamides
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Copper-mediated amidation of alkenylzirconocenes generated in situ from alkynes and zirconocenes with acyl azides is accomplished under mild conditions. The reaction can be used to prepare various enamides.
- Liu, Hailan,Zhou, Yiqing,Yan, Xiaoyu,Chen, Chao,Liu, Qingbin,Xi, Chanjuan
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- ISOINDOLINONE COMPOUNDS
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Disclosed herein is a compound or pharmaceutically acceptable salts or stereoisomers thereof of of formula I wherein X1 is linear or branched C1-6 alkyl, C3-6 cycloalkyl, -C1-6 alkyl C3-6 cycloalkyl, C6-10 aryl, 5-10 membered heteroaryl, C1-6 alkyl C6-10 aryl, C1-6 alkyl 5-10 membered heteroaryl, wherein X1 is unsubstituted or substituted with one or more of halogen, linear or branched C1-6 alkyl, linear or branched C1-6 heteroalkyl, CF3, CHF2, -O-CHF2, -O-(CH2)2-OMe, OCF3, C1-6 alkylamino, -CN, -N(H)C(O)-C1- 6alkyl, -OC(O)-C1-6alkyl, -OC(O)-C1-4alkylamino, -C(O)O-C1-6alkyl, -COOH, - CHO, -C1-6alkylC(O)OH, -C1-6alkylC(O)O-C1-6alkyl, NH2, C1-6 alkoxy or C1-6 alkylhydroxy; X2 is hydrogen, C6-10 aryl, 5-10 membered heteroaryl, -O-(5-10 membered heteroaryl), 4-8 membered heterocycloalkyl, C1-4 alkyl 4-8 membered heterocycloalkyl, -O-(4-8 membered heterocycloalkyl), -O-C1-4 alkyl-(4-8 membered heterocycloalkyl), -OC(O)-C1-4alkyl-4-8 membered heterocycloalkyl or C6 aryloxy, wherein X2 is unsubstituted or substituted with one or more of linear or branched C1-6 alkyl, NH2, NMe2 or 5-6 membered heterocycloalkyl; n is 0, 1 or 2.
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Page/Page column 170
(2021/04/17)
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- Synthesis of Acyl Phosphoramidates Employing a Modified Staudinger Reaction
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A one-step synthesis of acyl phosphoramidates from a variety of functionalized acyl azides has been developed employing trimethylsilyl chloride as an activating agent in a modified Staudinger reaction. The methodology was further adapted to include the in situ generation of the acyl azides from a diverse selection of carboxylic acids and hydrazide starting synthons. The reaction scope was extended to include the synthesis of imidodiphosphates and the natural product Microcin C.
- Currie, Iain,Sleebs, Brad E.
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supporting information
p. 464 - 468
(2021/02/03)
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- Synthesis of Acyl Azides from 1,3-Diketones via Oxidative Cleavage of Two C-C Bonds
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A metal-free PhI(OAc)2-mediated method for the synthesis of acyl azides through oxidative cleavage of 1,3-diketones is described. This method is shown to have a broad substrate scope, providing a useful tool for multiproduct synthesis in a single procedure. A possible reaction pathway is proposed based on mechanistic studies.
- Yu, Tian-Yang,Zheng, Zhao-Jing,Dang, Tong-Tong,Zhang, Fang-Xia,Wei, Hao
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p. 10589 - 10594
(2018/09/06)
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- Palladium-Catalyzed One-Pot Synthesis of N -Sulfonyl, N -Phosphoryl, and N -Acyl Guanidines
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An efficient palladium-catalyzed cascade reaction of azides with isonitrile and amines is presented; it offers an alternative facile approach toward N -sulfonyl-, N -phosphoryl-, and N -acyl-functionalized guanidines in excellent yield. These series of substituted guanidines exhibit potential biological and pharmacological activities. In addition, the less reactive intermediate benzoyl carbodiimide could be isolated by silica gel column flash chromatography in moderate yield.
- Qiao, Guanyu,Zhang, Zhen,Huang, Baoliang,Zhu, Liu,Xiao, Fan,Zhang, Zhenhua
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supporting information
p. 330 - 340
(2018/01/12)
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- Unprecedented Transformation of a Directing Group Generated in Situ and Its Application in the One-Pot Synthesis of 2-Alkenyl Benzonitriles
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An unprecedented protocol for the transformation of benzoyl azides into benzonitrile derivatives via iminophosphoranes generated in situ is described. The strategy was successfully applied to the de-novo synthesis of 2-alkenylated benzonitrile derivatives from benzoyl azides through ortho CH activation/alkenylation followed by subsequent rearrangement. The salient features of this protocol involve incorporation of two important functionalities through cyanation and olefination in one pot under mild reaction conditions by using a less expensive Ru catalyst. The mechanism was established by isolating and characterising (using 31PNMR) an intermediate with two ortho functionalities, iminophosphorane and olefin, under specific reaction conditions. Directly functional! Cyanation and olefination was accomplished in one pot from benzoyl azides through an unprecedented directing group transformation. The method generates benzonitriles and can be used for the synthesis of 2-alkenylated benzonitrile derivatives (see scheme).
- Kumar, Ravi,Arigela, Rajesh K.,Kundu, Bijoy
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p. 11807 - 11812
(2015/08/11)
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- The challenge of palladium-catalyzed aromatic azidocarbonylation: From mechanistic and catalyst deactivation studies to a highly efficient process
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Azidocarbonylation of iodoarenes with CO and NaN3, a novel Heck-type carbonylation reaction, readily occurs in an organic solvent-H 2O biphasic system to furnish aroyl azides at room temperature and 1 atm. The reaction is catalyzed by Xantphos-Pd and exhibits high functional group tolerance. The catalyst deactivation product, [(Xantphos)PdI2], can be reduced in situ with PMHS to Pd(0) to regain catalytic activity. In this way, the catalyst loading has been lowered to 0.2% without any losses in selectivity at nearly 100% conversion to synthesize a series of aroyl azides in 80-90% isolated yield on a gram scale. Alternatively, the ArCON3 product can be used without isolation for further transformations in situ, e.g., to isocyanates, ureas, benzamides, and iminophosphoranes. A detailed experimental and computational study has identified two main reaction pathways for the reaction. For both routes, Ar-I oxidative addition to Pd(0) is the rate-determining step. In the presence of CO in excess, the Ar-I bond is activated by the less electron-rich Pd center of a mixed carbonyl phosphine complex. Under CO-deficient conditions, a slightly lower energy barrier pathway is followed that involves Ar-I oxidative addition to a more reactive carbonyl-free (Xantphos)Pd0 species. Mass transfer in the triphasic liquid-liquid-gas system employed for the reaction plays an important role in the competition between these two reaction channels, uniformly leading to a common aroyl azido intermediate that undergoes exceedingly facile ArCO-N 3 reductive elimination. Safety aspects of the method have been investigated.
- Miloserdov, Fedor M.,McMullin, Claire L.,Belmonte, Marta Martinez,Benet-Buchholz, Jordi,Bakhmutov, Vladimir I.,Macgregor, Stuart A.,Grushin, Vladimir V.
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supporting information
p. 736 - 752
(2014/03/21)
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- NOVEL UREA DERIVATIVES AS TEC KINASE INHIBITORS AND USES THEREOF
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Provided are urea compounds of formula (I) as Tec kinase inhibitors, in particular ITK (interleukin-2 inducible tyrosine kinase) inhibitors. Also provided herein are processes for preparing compounds described herein, intermediates used in their synthesis, pharmaceutical compositions thereof, and methods for treating or preventing diseases, conditions and/or disorders mediated by ITK.
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Page/Page column 53; 54
(2013/03/26)
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- A simple, one-pot synthesis of N-Alkyl and N-aryl thieno[2,3-d] pyrimidinones from thiophene-and benzothiophene-2-yl-ureas
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We herein describe a convenient, one-pot synthesis of N-substituted thieno and benzothieno[2,3-d]pyrimidinones from the respective thiophene-2-yl ureas. This intramolecular cyclization, which presumably proceeds via a Vilsmeier-Haack dimethyliminium inter
- Yule, Ian A.,Fishwick, Colin W. G.
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p. 337 - 344,8
(2020/10/15)
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- Palladium-catalyzed aromatic azidocarbonylation
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Aryl iodides smoothly react with NaN3 and CO in the presence of a Pd/Xantphos catalyst to give aroyl azides (ArCON3) in 75-92 % yield. The reaction occurs under mild reaction conditions (1 atm, 20-50 °C) and exhibits high functional-group tolerance. (Xantphos=9,9-dimethyl-4,5- bis(diphenylphosphino)xanthene)
- Miloserdov, Fedor M.,Grushin, Vladimir V.
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supporting information; experimental part
p. 3668 - 3672
(2012/05/20)
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- Application of 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate (TBTU) for the synthesis of acid azides
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Conversion of acids to acyl azides using peptide coupling agent TBTU has been demonstrated. The procedure is simple and applicable to a range of carboxylic acids under mild reaction conditions. The protocol is extended to the synthesis of urethane protect
- Naik, Shankar A.,Lalithamba,Sureshbabu, Vommina V.
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scheme or table
p. 103 - 109
(2011/04/15)
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- New and simple synthesis of acid azides, ureas and carbamates from carboxylic acids: Application of peptide coupling agents EDC and HBTU
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Conversion of carboxylic acids into acid azides using peptide coupling agents, EDC and HBTU is described. The procedure is efficient, practical and applicable to a diverse range of carboxylic acids including N-protected amino acids. Using the same reagents, one-pot synthesis of ureas, dipeptidyl urea esters and carbamates from acids has also been achieved. The Royal Society of Chemistry 2010.
- Sureshbabu, Vommina V.,Lalithamba,Narendra,Hemantha
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experimental part
p. 835 - 840
(2010/06/20)
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- T3P (propylphosphonic anhydride) mediated conversion of carboxylic acids into acid azides and one-pot synthesis of ureidopeptides
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A general, mild, efficient, and environmentally benign protocol, which makes use of T3P as an acid activating agent for the direct synthesis of acid azides from carboxylic acids is described. Further, the protocol is employed for the one-pot synthesis of α-ureidopeptides starting from N-protected α-amino acids.
- Basavaprabhu,Narendra,Lamani, Ravi S.,Sureshbabu, Vommina V.
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experimental part
p. 3002 - 3005
(2010/07/10)
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- Preparation of polyfunctional acyl azides
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(Chemical Equation Presented) A general synthesis of acyl azides from the corresponding N-acyl benzotriazoles is described. The procedure affords acyl azides in good yields and avoids the use of acid activators and NO+ equivalents typically emp
- Katritzky, Alan R.,Widyan, Khalid,Kirichenko, Kostyantyn
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p. 5802 - 5804
(2008/02/09)
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- Tyrosine kinase inhibitors. 4. Structure-activity relationships among N- and 3-substituted 2,2'-dithiobis(1H-indoles) for in vitro inhibition of receptor and nonreceptor protein tyrosine kinases
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A series of 3-substituted 2,2'-dithiobis(1H-indoles) were synthesized and evaluated for their ability to inhibit the tyrosine kinase activity of both the epidermal growth factor receptor (EGFR) and the nonreceptor pp60(v-src) tyrosine kinase, to extend the available structure-activity relationships for this series. The majority of the compounds were prepared either by reaction of 2-chloro-1-methylindole-3-carbonyl chloride with amines, followed by thiomethylation, demethylation, and oxidative dimerization, or by reaction of isocyanates with the anion of 1-methyl-2-indolinethione followed by dimerization. Overall, inhibitory activity is retained by analogues having a wide variety of side chains. A series of 3-carboxamide analogues had moderate to good activity against isolated EGFR (IC50s 1-20 μM), with monoalkyl substitution of the carboxamide being optimal. Polar side chains were generally less effective than lipophilic ones, with benzyl being particularly effective. However, N,N-disubstitution was the most effective pattern for inhibition of pp60(v-src). A variety of substituted N-phenylcarboxamides had lower activity against EGFR than the parent derivative, and a N- thienylcarboxamide also had low activity. A series of 3-ketones, including methyl, phenyl, and furyl derivatives, showed moderate activity against the pp60(v-src) kinase, but were less effective against EGFR. The mechanism of inhibition of both kinases by these drugs was shown to be noncompetitive with respect to both ATP and peptide substrate. Selected compounds inhibited the growth of Swiss 3T3 cells with IC50s in the low micromolar range and inhibited bFGF-mediated intracellular tyrosine phosphorylation in the same cell line. Thiol inhibits the effects of the compounds, suggesting that one possible mechanism of inhibition is thiol-disulfide exchange with thiol- containing residues in the catalytic sites. Crystal structures of two representative compounds show a folded, V-shaped structure, with the disulfide bridge exposed, consistent with this hypothesis.
- Palmer,Rewcastle,Thompson,Boyd,Showalter,Sercel,Fry,Kraker,Denny
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- Preparation and Cycloaddition of Thienyl Isocyanates with Trimethylsilyl Azide: One-pot Synthesis of Thienyltetrazolin-5-ones
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Efforts to prepare thienyl isocyanates by thermal reactions of thenoyl chlorides with trimethylsilyl azide (TMSA) led preferentially to the formation of 1,4-disubstituted tetrazolin-5-ones, arising by interaction of the initially formed thienyl isocyanate with TMSA.In fact, 2-thenoyl chloride and benzothiophene-2-carbonyl chloride reacted with 1 equiv.TMSA in refluxing carbon tetrachloride to give 1-(2-thienyl or benzothienyl)-4-(2-thenoyl or benzothiophenecarbonyl)tetrazolin-5-one 4d, e, whereas 3-thenoyl chloride led to 1-(3-thienyl)-4-trimethylsilyltetrazolin-5-one adduct II which was converted, after hydrolytic desilylation, to 1-(3-thienyl)tetrazolin-5(4H)-one 4c.Similar reactions, carried out with more than two equiv. of TMSA, led in all cases to the formation of the corresponding 1-heteroaryltetrazolin-5-one 4a-c via the corresponding silylated tetrazolin-5-ones II, whereas at room temp. such reactions gave essentially thenoyl azides which, after elimination of the excess TMSA, were thermally converted to the corresponding thienyl isocyanates 3 in fairly good yields.
- Toselli, Maurizio,Zanirato, Paolo
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p. 1101 - 1104
(2007/10/02)
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