Towards potential nanoparticle contrast agents: Synthesis of new functionalized PEG bisphosphonates

• Souad Kachbi-Khelfallah,
• Maelle Monteil,
• Margery Cortes-Clerget,
• Evelyne Migianu-Griffoni,
• Jean-Luc Pirat,
• Olivier Gager,
• Julia Deschamp and
• Marc Lecouvey

Beilstein J. Org. Chem. 2016, 12, 1366–1371, doi:10.3762/bjoc.12.130

• yields (Table 1, entries 5–7). Finally, the optimized two-step procedure enabled us to isolate the expected carboxylic acids 6 and 7a,b which are key intermediates in the synthesis of PEG-HMBPs. The carboxylic acids 6 and 7a,b reacted quantitatively with oxalyl chloride to give acyl chlorides 8 and 9a,b

Copper-catalyzed [3 + 2] cycloaddition of (phenylethynyl)di-p-tolylstibane with organic azides

• Mizuki Yamada,
• Mio Matsumura,
• Yuki Uchida,
• Masatoshi Kawahata,
• Yuki Murata,
• Naoki Kakusawa,
• Kentaro Yamaguchi and
• Shuji Yasuike

Beilstein J. Org. Chem. 2016, 12, 1309–1313, doi:10.3762/bjoc.12.123

• organoantimony compounds in organic synthesis has attracted much interest during the last two decades [25][26]. Trivalent organoantimony compounds (stibanes) such as aryl- and ethynylstibanes are useful transmetalation agents in Pd-catalyzed cross-coupling reactions with aryl halides and acyl chlorides [27][28

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

• Mohammad Haji

Beilstein J. Org. Chem. 2016, 12, 1269–1301, doi:10.3762/bjoc.12.121

• acyl chlorides 191, isocyanides 193 and dialkyl acetylenedicarboxylates 194 to afford 2-phosphonofuran derivatives 196 has been reported by our group (Scheme 41) [79]. The desired furanylphosphonates were isolated in 52–67% yield at rt in CH2Cl2. In this transformation the zwitterionic intermediate 195

• ) [88]. Further, 1-acyl-1,2-dihydroquinoline-2-phosphonates 251 and 2-acyl-1,2-dihydroisoquinoline-1-phosphonates 252 have been prepared via the one-pot reaction of quinoline (242) or isoquinolines 249 with acyl chlorides 250 and trimethyl phosphite in the presence of NaI in 22–94% yields depending on

• the nature of the acyl chlorides and substituents X (Scheme 52) [89][90]. The three-component reaction of dimethyl phosphite, acetyl chloride and isoquinoline under refluxing in CH2Cl2 in the presence or absence of triethylamine led to the desired 1,2-dihydroisoquinoline-1-phosphonates in 66% and 45

Synthesis of β-arylated alkylamides via Pd-catalyzed one-pot installation of a directing group and C(sp³)–H arylation

• Yunyun Liu,
• Yi Zhang,
• Xiaoji Cao and
• Jie-Ping Wan

Beilstein J. Org. Chem. 2016, 12, 1122–1126, doi:10.3762/bjoc.12.108

• .12.108 Abstract The synthesis of β-arylated alkylamides via alkyl C–H bond arylation has been realized by means of direct one-pot reactions of acyl chlorides, aryl iodides and 8-aminoquinoline. Depending on the structure of the starting materials, both single and double β-arylated alkylamides could be

• DG to reactants is required in most of presently known DG-assisted reactions. For example, in the widely studied reactions employing AQ (8-aminoquinoline) as DG, the prior reaction (including isolation) of the corresponding acyl chlorides and AQ is generally the mandatory procedure before conducting

• reaction temperature indicated that 120 °C was the favorable temperature (entries 16 and 17, Table 1). Following the above optimization experiments, the scope of this one-pot approach in the synthesis of arylated amides was then examined by subjecting different aryl iodides and acyl chlorides. According to

C–H bond halogenation catalyzed or mediated by copper: an overview

• Wenyan Hao and
• Yunyun Liu

Beilstein J. Org. Chem. 2015, 11, 2132–2144, doi:10.3762/bjoc.11.230

• rate-limiting step. In 2011, Cheng and co-workers discovered an alternative route of a C–H chlorination protocol of 2-arylpyridines by employing acyl chlorides 6 as chlorinating reagents [33]. A range of mono-chlorinated 2-arylpridines 2 were obtained in the presence of Cu(OAc)2 and Li2CO3 under O2

• , the unavailability of a practical copper-catalyzed halogenation of alkyne C(sp)–H bonds is also an issue requiring urgent attention. Copper-catalyzed C–H bond halogenation of 2-arylpyridine. ortho-Chlorination of 2-arylpridines with acyl chlorides. Copper-catalyzed chlorination of 2-arylpyridines

Tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds

• Javier Miró,
• María Sánchez-Roselló,
• Álvaro Sanz,
• Fernando Rabasa,
• Carlos del Pozo and
• Santos Fustero

Beilstein J. Org. Chem. 2015, 11, 1486–1493, doi:10.3762/bjoc.11.161

• 5 (method A) or acyl chlorides 6 (method B) under standard conditions (Scheme 3). Since the basic indole nitrogen in substrate 8f could interfere with the ruthenium catalyst, it was N-methylated to render compound 8g. With substrates 8 in hand, they were subjected to the optimized conditions of the

One-pot odourless synthesis of thioesters via in situ generation of thiobenzoic acids using benzoic anhydrides and thiourea

• Mohammad Abbasi and
• Reza Khalifeh

Beilstein J. Org. Chem. 2015, 11, 1265–1273, doi:10.3762/bjoc.11.141

• preparation of alkane thiols using thiourea and alkyl halides is a well-known reaction in organic synthesis. In addition, two methods for the synthesis of thioacids from acyl chlorides using N,N-dimethylthioformamide [51] or thioacetamide [52] have been reported. As far as we know, a similar reaction using

• propargylic halides have been easily converted to the related thioesters within appropriate reaction times in good to excellent yields (Table 2, entries 1–20). A general pathway for the reaction has been proposed as presented in Scheme 3. Similar to reactions of acyl chlorides with N,N-dimethylthioformamide

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

• Tor E. Kristensen

Beilstein J. Org. Chem. 2015, 11, 446–468, doi:10.3762/bjoc.11.51

• crystalline hydrochloride salts may be precipitated directly from the medium in acylation reactions employing acyl chlorides. The eventual identification of anhydrous trifluoroacetic acid (CF3CO2H) as perhaps the most appropriate reaction medium identified so far for such acidic acylation reactions will

• of their method through the possibility of employing other acyl chlorides than acetyl chloride, this work apparently did not trigger a decisive breakthrough in the widespread application of acidic chemoselective O-acylation methodologies in organic synthesis. Although speculative, the origin of the

• of N-acetylglucosamine) by O-acylation, using carboxylic anhydrides or acyl chlorides in methanesulfonic acid solution [31][32][33]. Taking inspiration from these disclosures, Kawasaki and Komai then, in 1983, reported on the chemoselective O-acylation of hydroxyproline with carboxylic anhydrides or

The preparation of new functionalized [2.2]paracyclophane derivatives with N-containing functional groups

• Henning Hopf,
• Swaminathan Vijay Narayanan and
• Peter G. Jones

Beilstein J. Org. Chem. 2015, 11, 437–445, doi:10.3762/bjoc.11.50

• most other acyl chlorides, 26 is a stable compound with a high melting point (210 °C), which could easily be recrystallized from dichloromethane/pentane to furnish single crystals suitable for X-structural analysis. The molecule of 26 (Figure 5) possesses crystallographic inversion symmetry, consistent

Natural phenolic metabolites with anti-angiogenic properties – a review from the chemical point of view

• Qiu Sun,
• Jörg Heilmann and
• Burkhard König

Beilstein J. Org. Chem. 2015, 11, 249–264, doi:10.3762/bjoc.11.28

•  7). Compounds 30–34 were obtained through Friedel–Crafts acylation of 29 with corresponding acyl chlorides in 55–81% yield. Subsequent alkylation with geranyl bromide gave products 35–39 in moderate yields from 55 to 60%. Finally, p-toluenesulfonic acid (pTSA)-catalyzed cyclization afforded the

Synthesis of dinucleoside acylphosphonites by phosphonodiamidite chemistry and investigation of phosphorus epimerization

• William H. Hersh

Beilstein J. Org. Chem. 2015, 11, 184–191, doi:10.3762/bjoc.11.19

• William H. Hersh Department of Chemistry and Biochemistry, Queens College and the Graduate Center of the City University of New York, Queens, NY 11367-1597, USA 10.3762/bjoc.11.19 Abstract The reaction of the diamidite, (iPr2N)2PH, with acyl chlorides proceeds with the loss of HCl to give the

Efficient deprotection of F-BODIPY derivatives: removal of BF₂ using Brønsted acids

• Mingfeng Yu,
• Joseph K.-H. Wong,
• Cyril Tang,
• Peter Turner,
• Matthew H. Todd and
• Peter J. Rutledge

Beilstein J. Org. Chem. 2015, 11, 37–41, doi:10.3762/bjoc.11.6

• diversifying the F-BODIPY framework [9]. F-BODIPYs are readily prepared by condensing aldehydes, acyl chlorides or anhydrides with pyrroles and trapping the resulting dipyrrin in situ with boron trifluoride [9][10][11]. F-BODIPYs are generally stable and chemically robust, with photophysical properties that

Non-cross-linked polystyrene-supported 2-imidazolidinone chiral auxiliary: synthesis and application in asymmetric alkylation reactions

• Quynh Pham Bao Nguyen and
• Taek Hyeon Kim

Beilstein J. Org. Chem. 2013, 9, 2113–2119, doi:10.3762/bjoc.9.248

• of t-BuOK in THF (5 equiv) was added dropwise, followed by the addition of acyl chlorides (10 equiv). The reaction mixtures were stirred for 30 min, quenched by adding saturated NH4Cl solution and extracted with CH2Cl2. The organic layers were evaporated and the obtained viscous solutions were

Enantioselective reduction of ketoimines promoted by easily available (S)-proline derivatives

• Martina Bonsignore,
• Maurizio Benaglia,
• Laura Raimondi,
• Manuel Orlandi and
• Giuseppe Celentano

Beilstein J. Org. Chem. 2013, 9, 633–640, doi:10.3762/bjoc.9.71

• reduction at 0 °C. The easy one-step reaction between (S)-proline and various acyl chlorides, in the presence of 1 N NaOH, allowed the formation of the catalysts illustrated in Figure 4. The acyl chlorides, when not commercially available, were prepared starting from the corresponding acid by treatment with

Similarity analysis, synthesis, and bioassay of antibacterial cyclic peptidomimetics

• Workalemahu M. Berhanu,
• Mohamed A. Ibrahim,
• Girinath G. Pillai,
• Alexander A. Oliferenko,
• Levan Khelashvili,
• Farukh Jabeen,
• Bushra Mirza,
• Farzana Latif Ansari,
• Ihsan ul-Haq,
• Said A. El-Feky and
• Alan R. Katritzky

Beilstein J. Org. Chem. 2012, 8, 1146–1160, doi:10.3762/bjoc.8.128

• direction of the two chains attached to the cysteine residue. For example, one of the early cysteine-containing macrocycles was designed to mimic the cation binding ability of valinomycin [24]. Numerous literature approaches to the synthesis of 17-, 18- and 24-membered rings utilize: (i) acyl chlorides, (ii

Synthesis and characterization of Sant-75 derivatives as Hedgehog-pathway inhibitors

• Chao Che,
• Song Li,
• Bo Yang,
• Shengchang Xin,
• Zhixiong Yu,
• Taofeng Shao,
• Chuanye Tao,
• Shuo Lin and
• Zhen Yang

Beilstein J. Org. Chem. 2012, 8, 841–849, doi:10.3762/bjoc.8.94

• , such as polar and hydrophobic groups, were introduced to the phenyl ring in motif A. Scheme 2 described the synthesis of derivatives 7a–l through the reaction of compound 4 with a number of substituted acyl chlorides 6a–l, which were prepared from the corresponding cinnamic acids by Higa cyclization

• compounds as Hedgehog-pathway inhibitors. Therefore, the emphasis of the fourth series of structural optimization was placed on the nitrogen atom through capping of the amino group with various acyl chlorides, delivering the corresponding amides 21a–j. It should be noted that the capping of the amino group

Alkoxide-induced ring opening of bicyclic 2-vinylcyclobutanones: A convenient synthesis of 2-vinyl-substituted 3-cycloalkene-1-carboxylic acid esters

• Xiufang Ji,
• Zhiming Li,
• Quanrui Wang and
• Andreas Goeke

Beilstein J. Org. Chem. 2012, 8, 650–657, doi:10.3762/bjoc.8.72

• reaction involves generation of the intermediate vinylketenes or phenylketenes by the triethylamine-promoted 1,4- or 1,2-dehydrochlorination of acyl chlorides 2 [1]. The in situ generated vinylketenes or phenylketenes 3 were trapped by reaction with excessive amount of alkenes 1 in methylene chloride. The

Cyclization of 5-hexynoic acid to 3-alkoxy-2-cyclohexenones

• Anne T. Hylden,
• Eric J. Uzelac,
• Zeljko Ostojic,
• Ting-Ting Wu,
• Keely L. Sacry,
• Krista L. Sacry,
• Lin Xi and
• T. Nicholas Jones

Beilstein J. Org. Chem. 2011, 7, 1323–1326, doi:10.3762/bjoc.7.155

• -cyclohexenones. Keywords: acyl chlorides; alcohols; alkynes; cyclization; Lewis acids; Findings Synthetic applications of 3-alkoxy-2-cyclohexenones toward the pursuit of natural products have been well documented [1][2][3][4]. Traditionally, 3-alkoxy-2-cyclohexenones have been prepared from 1,3-cyclohexadiones

A practical route to tertiary diarylmethylamides or -carbamates from imines, organozinc reagents and acyl chlorides or chloroformates

• Erwan Le Gall,
• Antoine Pignon and
• Thierry Martens

Beilstein J. Org. Chem. 2011, 7, 997–1002, doi:10.3762/bjoc.7.112

• -carbamates from imines, organozinc reagents and acyl chlorides or chloroformates is described. This route involves the formation of an imine, which is used without isolation, followed by its activation by the carbonyl-containing electrophile and the trapping of the acyliminium by an organozinc reagent. Most

Synthesis of novel 5-alkyl/aryl/heteroaryl substituted diethyl 3,4-dihydro-2H-pyrrole-4,4-dicarboxylates by aziridine ring expansion of 2-[(aziridin-1-yl)-1-alkyl/aryl/heteroaryl-methylene]malonic acid diethyl esters

• Satish S. More,
• T. Krishna Mohan,
• Y. Sateesh Kumar,
• U. K. Syam Kumar and
• Navin B. Patel

Beilstein J. Org. Chem. 2011, 7, 831–838, doi:10.3762/bjoc.7.95

• -chloromethylene)malonates 19. The chloro alkenyl malonates 19 were synthesized in two steps from diethyl malonate and acid chlorides. The acylation of diethyl malonate was carried out with various acyl chlorides in the presence of anhydrous magnesium chloride and triethylamine, as per the reaction conditions

• conditions: i) THF, rt, 3 h; ii) NaI, acetone, rt, overnight. Reaction conditions: i) THF, TEA, rt; ii) NaI, acetone, rt, overnight. Synthesis of N-vinylaziridines from diethyl malonate and acyl chlorides. Iodide ion mediated ring expansion of N-vinylaziridines. Supporting Information Supporting Information

Homoallylic amines by reductive inter- and intramolecular coupling of allenes and nitriles

• Peter Wipf and
• Marija D. Manojlovic

Beilstein J. Org. Chem. 2011, 7, 824–830, doi:10.3762/bjoc.7.94

• range of electrophiles to form imine derivatives [28][29][30]. Floreancig and co-workers developed a method for the preparation of α-functionalized amides by trapping N-zirconoimines with acyl chlorides, followed by the addition of nucleophiles to the intermediate acyl imines [31][32][33]. Furthermore

2-Phenyl- tetrahydropyrimidine- 4(1H)-ones – cyclic benzaldehyde aminals as precursors for functionalised β²-amino acids

• Markus Nahrwold,
• Arvydas Stončius,
• Anna Penner,
• Beate Neumann,
• Hans-Georg Stammler and
• Norbert Sewald

Beilstein J. Org. Chem. 2009, 5, No. 43, doi:10.3762/bjoc.5.43

• consists of a 4-DMAP catalysed N-acylation reaction with acyl chlorides and usually affords the target compounds in moderate yields [39][40]. We chose Nα-Cbz-protected β-alanine amide (3) as starting material for the synthesis of the 2-phenyltetrahydropyrimidine-4(1H)-one rac-4 to circumvent the difficulty

Synthesis of the Benzo- fused Indolizidine Alkaloid Mimics

• Daniel L. Comins and
• Kazuhiro Higuchi

Beilstein J. Org. Chem. 2007, 3, No. 42, doi:10.1186/1860-5397-3-42

• biological activity. The various kinds of N-acyldihydropyridones 1 were conveniently prepared from heteroaryl Grignard reagents and N-acylpyridinium salts. Subsequently, dihydropyridones 1 were converted to 8 by use of an intramolecular Heck cyclization. The chloro- and nitro-substituted acyl chlorides 7

Synthesis of phosphorothioates using thiophosphate salts

• Babak Kaboudin and
• Fatemeh Farjadian

Beilstein J. Org. Chem. 2006, 2, No. 4, doi:10.1186/1860-5397-2-4

• and chemoselective thioacylating agent using the reaction of acyl chlorides with dithiophosphoric acid in the presence of pyridine or triethylamine. [51][52][53] In another study we decided to investigate the reaction of the ambident nucleophile ammonium O,O'-diethyl thiophosphate salt with acyl

• chlorides. Reaction of ammonium O,O'-diethyl thiophosphate with benzoyl chloride, as a model compound, in acetonitrile gave benzamide as the major product (Scheme 5). Benzoyl chloride reacts with ammonia (from ammonium O,O'-diethyl thiophosphate) faster than anion O,O'-diethyl thiophosphate to give