(E,Z)-1,1,1,4,4,4-Hexafluorobut-2-enes: hydrofluoroolefins halogenation/dehydrohalogenation cascade to reach new fluorinated allene

• Nataliia V. Kirij,
• Andrey A. Filatov,
• Yurii L. Yagupolskii,
• Sheng Peng and
• Lee Sprague

Beilstein J. Org. Chem. 2024, 20, 452–459, doi:10.3762/bjoc.20.40

• conclusion, we synthesized a series of synthons from available industrial starting compounds – (E,Z)-1,1,1,4,4,4-hexafluorobut-2-enes (1a,b) using simple procedures. We demonstrated the halogenation reactions of butenes 1a,b with bromine and iodine monochloride to form 2,3-dihalo-1,1,1,4,4,4

• iodine monochloride were also studied. Synthesis of 2,3-dibromo-1,1,1,4,4,4-hexafluorobutane (2). Synthesis of (E)-butene 3a. Isomerization reaction of (E)-butene 3a to (Z)-butene 3b. Synthesis of 2-chloro-3-iodo-1,1,1,4,4,4-hexafluorobutane (5). Dehydrohalogenation reaction of 2-chloro-3-iodo

• presence of SbCl5, AlCl3, Bu4NOH/MeOH and under UV irradiation. We found that under UV irradiation for several hours, the (E)-isomer 3a completely transformed into (Z)-isomer 3b in quantitative yield (Scheme 3). Next, our attention was directed toward the reaction of (E)- and (Z)-butenes 1a,b with iodine

Progress in the total synthesis of inthomycins

• Bidyut Kumar Senapati

Beilstein J. Org. Chem. 2021, 17, 58–82, doi:10.3762/bjoc.17.7

• access to dienylboronate (rac)-19a in 43% yield. A competitive Suzuki coupling was also observed with compound (rac)-19b being isolated in 35% yield [32][33][34][35]. Dienylboronate (rac)-19a was then transformed into dienyl iodide (rac)-20 by iodine monochloride addition and methoxide-mediated

Synthesis of tetrafluorinated piperidines from nitrones via a visible-light-promoted annelation reaction

• Vyacheslav I. Supranovich,
• Igor A. Dmitriev and
• Alexander D. Dilman

Beilstein J. Org. Chem. 2020, 16, 3104–3108, doi:10.3762/bjoc.16.260

• iodine by treatment with zinc, followed by the reaction with iodine monochloride. The iodide 2b reacted quite rapidly with the nitrone but the expected fluoroalkylation product was not observed. Instead, the tetrafluorinated piperidine 3a was obtained in a moderate yield (Table 1, entry 2). Apparently

Pentannulation of N-heterocycles by a tandem gold-catalyzed [3,3]-rearrangement/Nazarov reaction of propargyl ester derivatives: a computational study on the crucial role of the nitrogen atom

• Giovanna Zanella,
• Martina Petrović,
• Dina Scarpi,
• Ernesto G. Occhiato and
• Enrique Gómez-Bengoa

Beilstein J. Org. Chem. 2020, 16, 3059–3068, doi:10.3762/bjoc.16.255

• acid, as previously reported [45]. In the next step, the electrophilic addition of iodine monochloride to the double bond of the enesulfonamide 10, followed by a nucleophilic attack of methanol on the formed iodonium ion afforded the α-methoxy-β-iodopiperidine 11 as a single stereoisomer (91% yield

Ring-size-selective construction of fluorine-containing carbocycles via intramolecular iodoarylation of 1,1-difluoro-1-alkenes

• Takeshi Fujita,
• Ryo Kinoshita,
• Tsuyoshi Takanohashi,
• Naoto Suzuki and
• Junji Ichikawa

Beilstein J. Org. Chem. 2017, 13, 2682–2689, doi:10.3762/bjoc.13.266

• ) triflate improved the yield of 2a (Table 1, entries 2 and 3). Although iodine monochloride, which is known as a cationic iodine species, afforded only ketone 3a (Table 1, entry 4), its pyridine complex (PyICl) exclusively afforded the iodoarylation product 2a in 31% yield (Table 1, entry 5). The use of a 9

• without further purifications. Typical procedure for the iodoarylation of 2-(2-aryl-3,3-difluoroallyl)biaryls 1: To a HFIP (1.20 mL) and dichloromethane (0.13 mL) solution of 2-(2-phenyl-3,3-difluoroallyl)biphenyl (1a, 31 mg, 0.10 mmol) was added pyridine iodine monochloride (PyICl, 49 mg, 0.20 mmol) at 0

High performance p-type molecular electron donors for OPV applications via alkylthiophene catenation chromophore extension

• Paul B. Geraghty,
• Calvin Lee,
• Jegadesan Subbiah,
• Wallace W. H. Wong,
• James L. Banal,
• Mohammed A. Jameel,
• Trevor A. Smith and
• David J. Jones

Beilstein J. Org. Chem. 2016, 12, 2298–2314, doi:10.3762/bjoc.12.223

• hexyl-substituted quater- and quinquethiophenes 8b and 10b, Scheme 2. Conversion of the intermediate TMS-protected oligothiophenes to the iodo-oligothiophenes (n =1 and 2) was achieved using iodine monochloride (ICl), however for n = 3 and 4 a number of side reactions leading to unidentified side

Properties of PTFE tape as a semipermeable membrane in fluorous reactions

• Brendon A. Parsons,
• Olivia Lin Smith,
• Myeong Chae and
• Veljko Dragojlovic

Beilstein J. Org. Chem. 2015, 11, 980–993, doi:10.3762/bjoc.11.110

• uptake of the solvent resumes (Figure 7). By having the delivery tube just touch the surface of the solution in the reaction vessel, one can almost completely eliminate the solvent uptake as demonstrated by the PV-PTFE iodolactonization of the unsaturated diester 1 with iodine monochloride in

• bromine stirred by a cut stirring bar with the iron core exposed (three trials shown). Iodolactonization of unsaturated diester 1 with iodine monochloride in dichlormethane. Chemiluminescence reaction of diaryl oxalate esters oxidized by hydrogen peroxide in the presence of rubrene. Supporting

Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition

• Regina Berg and
• Bernd F. Straub

Beilstein J. Org. Chem. 2013, 9, 2715–2750, doi:10.3762/bjoc.9.308

• Sharpless and Fokin devised a new protocol starting from 1-iodoalkynes [156]. The great advantage compared to the procedures of Wu [157], Hsung [158] and Li [159] is that neither reactive electrophilic halogenating agents (such as NBS or iodine monochloride) nor stoichiometric amounts of copper salts need

AgOTf-catalyzed one-pot reactions of 2-alkynylbenzaldoximes with α,β-unsaturated carbonyl compounds

• Qiuping Ding,
• Dan Wang,
• Puying Luo,
• Meiling Liu,
• Shouzhi Pu and
• Liyun Zhou

Beilstein J. Org. Chem. 2013, 9, 1949–1956, doi:10.3762/bjoc.9.231

• progress in this aspect. Wu and co-workers described an efficient three-component reaction of a 2-alkynylbenzaldoxime and an α,β-unsaturated carbonyl compound with bromine or iodine monochloride under mild conditions, which generates the 1-alkylated isoquinolines in good to excellent yields [36]. Wu and co

Asymmetric total synthesis of smyrindiol employing an organocatalytic aldol key step

• Dieter Enders,
• Jeanne Fronert,
• Tom Bisschops and
• Florian Boeck

Beilstein J. Org. Chem. 2012, 8, 1112–1117, doi:10.3762/bjoc.8.123

• salicylaldehyde (Scheme 6). The total synthesis of smyrindiol is depicted in Scheme 7. Firstly, the O-acetonyl-salicylaldehyde 13, as the substrate for the aldol reaction, was synthesized in five steps. Iodination of commercially available 2,4-dihydroxybenzaldehyde (9) with iodine monochloride in acetic acid [11

Synthesis, reactivity and biological activity of 5-alkoxymethyluracil analogues

• Lucie Brulikova and
• Jan Hlavac

Beilstein J. Org. Chem. 2011, 7, 678–698, doi:10.3762/bjoc.7.80

• iodine monochloride and alcohols such as ethanol, 2-fluoroethanol or 2,2,2-trifluoroethanol afforded 5-(1-ethoxy-2,2-diiodoethyl) 33 and 5-(1-alkoxy-2-iodoethyl)-2'-deoxyuridines 34–36, in 33–90% yields. All of these four products 33–36 were obtained as a mixture of two diastereomers in a 1:1 ratio. In

• (9) was used as the starting compound. The regiospecific reaction of the 5-vinyl-2'-deoxyuridine (9) with iodine monochloride in the presence of various alcohols afforded 2'-deoxynucleosides 50–54 in 24–52% yield. Uracil analogues: The syntheses of some of the aforementioned 2'-deoxyuridine analogues

• were also described for modified uracil derivatives. The first group of these derivatives is represented by alkoxyiodoethyl derivatives 56–59 prepared by the reaction of 5-vinyluracil (55) with iodine monochloride (Scheme 9) [11]. The reaction was carried out in the presence of ethanol, 2-fluoroethanol

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

• many side reactions. The indole core of rizatriptan can also be prepared by a palladium-catalysed coupling first reported by Larock [24]. The iodoaniline derivative 84 required for this approach can be readily synthesised from triazolomethyl aniline 83 by treatment with iodine monochloride in aqueous

A short synthesis of (±)-cherylline dimethyl ether

• Bhima Y. Kale,
• Ananta D. Shinde,
• Swapnil S. Sonar,
• Bapurao B. Shingate,
• Sanjeev Kumar,
• Samir Ghosh,
• Soodamani Venugopal and
• Murlidhar S. Shingare

Beilstein J. Org. Chem. 2009, 5, No. 80, doi:10.3762/bjoc.5.80

• slurry of sodium azide (1.3 g, 0.02 mol) in acetonitrile (30 mL) in an ice bath was added slowly iodine monochloride (2.16 g, 0.01 mol) in acetonitrile (30 mL). The reaction mixture was stirred for an additional 5–10 min and 3-(3,4-dimethoxyphenyl)-3-(4-methoxyphenyl)propanal (2.0 g, 0.006 mol) in

Solvent-free phase-vanishing reactions with PTFE (Teflon^®) as a phase screen

• Kevin Pels and
• Veljko Dragojlovic

Beilstein J. Org. Chem. 2009, 5, No. 75, doi:10.3762/bjoc.5.75

• two liquid phases [21]. PTFE offers some advantages compared to a liquid perfluoro phase screen: PTFE tape is inexpensive, easy to use and may be reused. In addition, experimental design is not dependent upon densities of the reactants. However, in some cases, such as when iodine monochloride was used

• resulted in formation of 2,4,6-tribromophenol (Table 2, entry 6). Bromination of 4-pentenoic acid (17) gave the corresponding lactone 18 as the major product accompanied by some dibromoacid 19 (Table 3, entry 1). Reaction of the same compound with iodine monochloride gave only the corresponding lactone in

• (24) and acrylic acid (25) were combined in a flask with stirring and a tube with iodine monochloride was inserted into the vapor phase above the reactants. The resulting iodolactone 26 was isolated in a modest yield (Table 3, entry 4). This reaction is already known to be a low yielding reaction [15

Controlling hazardous chemicals in microreactors: Synthesis with iodine azide

• Johan C. Brandt and
• Thomas Wirth

Beilstein J. Org. Chem. 2009, 5, No. 30, doi:10.3762/bjoc.5.30

• stable carbamoyl azides 4 as shown in Scheme 1. As sodium azide is poorly soluble in organic solvents, we decided to use tetrabutylammonium azide for the in situ generation of iodine azide. The reaction with iodine monochloride is rapid and after several minutes (depending on the flow rate) the aldehyde

• [24][25]. Highest yields were obtained with commercially available tetrabutylammonium azide (Aldrich), although great care has to be taken as this compound is very hygroscopic. Calculations indicate that the synthesis of iodine azide from trimethylsilyl azide and iodine monochloride is slightly

• ratio of about 1:3 of trimethylsilyl azide and trimethylsilyl chloride upon reaction with iodine monochloride. This mixture was not efficient in the reaction with aldehydes, only an unidentifiable mixture of products was obtained. The reactivity of carbamoyl azides is analogous to isocyanates, compound

Phase- vanishing halolactonization of neat substrates

• Nicole Windmon and
• Veljko Dragojlovic

Beilstein J. Org. Chem. 2008, 4, No. 29, doi:10.3762/bjoc.4.29

• bicyclic systems. Bromine (Br2) and iodine monochloride (ICl) are suitable electrophiles for bromolactonization and iodolactonization, respectively. Although in some cases iodine gave satisfactory yields of the corresponding iodolactone, it is generally inferior to iodine monochloride. Keywords: bromine

• ; halocyclization; halolactonization; iodine monochloride; phase-vanishing reactions; Introduction Phase-vanishing reactions, introduced by Ryu [1], Curran [1][2] and Verkade [3], are triphasic reactions, which involve a reagent, a substrate and a liquid perfluoroalkane. A more recent improvement of phase

• apparently unstable. Thus, the corresponding iodolactone 5, along with a number of unidentified byproducts, was observed in GC-MS analysis of the reaction mixture. Isolation of the reaction product was not attempted. When iodine monochloride was used in place of iodine, the reaction was fast and the