- A Practical, Large-Scale Synthesis of p -(Difluoroiodo)toluene (p -TolIF 2)
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p -(Difluoroiodo)toluene (p -TolIF 2) is a versatile fluorinating agent that acts as both a surrogate for elemental fluorine, and as a source of 'electrophilic' fluorine. Described here is a detailed three-step synthesis of p -TolIF 2/sub
- Murphy, Graham K.,Tao, Jason
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- Fluorohydration of alkynes via I(I)/I(III) catalysis
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Substrate specificity is ubiquitous in biological catalysis, but less pervasive in the realm of small-molecule catalysis. Herein, we disclose an intriguing example of substrate specificity that was observed whilst exploring catalysis-based routes to generate α-fluoroketones from terminal and internal alkynes under the auspices of I(I)/I(III) catalysis. Utilising p-TolI as an inexpensive organocatalyst with Selectfluor and amine/HF mixtures, the formation of protected α-fluoroketones from simple alkynes was realised. Whilst the transient p-TolIF2 species generated in situ productively engaged with pentynyl benzoate scaffolds to generate the desired α-fluoroketone motif, augmentation or contraction of the linker suppressed catalysis. The prerequisite for this substructure was established by molecular editing and was complemented with a physical organic investigation of possible determinants.
- Daniliuc, Constantin G.,Gilmour, Ryan,Neufeld, Jessica
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supporting information
p. 1627 - 1635
(2020/09/11)
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- Electrochemical Vicinal Difluorination of Alkenes: Scalable and Amenable to Electron-Rich Substrates
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Fluorinated alkyl groups are important motifs in bioactive compounds, positively influencing pharmacokinetics, potency and conformation. The oxidative difluorination of alkenes represents an important strategy for their preparation, yet current methods are limited in their alkene-types and tolerance of electron-rich, readily oxidized functionalities, as well as in their safety and scalability. Herein, we report a method for the difluorination of a number of unactivated alkene-types that is tolerant of electron-rich functionality, giving products that are otherwise unattainable. Key to success is the electrochemical generation of a hypervalent iodine mediator using an “ex-cell” approach, which avoids oxidative substrate decomposition. The more sustainable conditions give good to excellent yields in up to decagram scales.
- Doobary, Sayad,Sedikides, Alexi T.,Caldora, Henry P.,Poole, Darren L.,Lennox, Alastair J. J.
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supporting information
p. 1155 - 1160
(2019/12/11)
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- Photocatalytic Fluoro Sulfoximidations of Styrenes
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Reactions of difluoroiodotoluene with NH-sulfoximines provide new hypervalent iodine(III) reagents, which photocatalytically transfer a fluoro and a sulfoximidoyl group onto styrenes with high regioselectivity. The substrate scope is broad with respect to
- Bolm, Carsten,Ma, Ding,Tu, Yongliang,Wang, Chenyang
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p. 14134 - 14137
(2020/06/17)
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- Hypervalent Iodine(III)-Catalyzed Balz–Schiemann Fluorination under Mild Conditions
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An unprecedented hypervalent iodine(III) catalyzed Balz–Schiemann reaction is described. In the presence of a hypervalent iodine compound, the fluorination reaction proceeds under mild conditions (25–60 °C), and features a wide substrate scope and good functional-group compatibility.
- Xing, Bo,Ni, Chuanfa,Hu, Jinbo
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p. 9896 - 9900
(2018/07/31)
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- Deconstructing the Catalytic, Vicinal Difluorination of Alkenes: HF-Free Synthesis and Structural Study of p-TolIF2
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Recently, contemporaneous strategies to achieve the vicinal difluorination of alkenes via an I(I)/I(III) catalysis manifold were independently reported by this laboratory and by Jacobsen and co-workers. Both strategies proceed through a transient ArI(III)
- Sarie, Jér?me C.,Thiehoff, Christian,Mudd, Richard J.,Daniliuc, Constantin G.,Kehr, Gerald,Gilmour, Ryan
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p. 11792 - 11798
(2017/11/24)
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- Geminal difunctionalization of α-diazo arylmethylphosphonates: Synthesis of fluorinated phosphonates
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A general approach towards diverse fluorinated phosphonates via geminal difunctionalization reactions of α-diazo arylmethylphosphonates is described. The diazo functionality (RR′CN2) is successfully converted to RR′CF2, RR′CHF, RR′CFBr or RR′CFNR′′2 groups by employing different fluorination reagents. A variety of fluorinated organophosphorus compounds were readily accessed in good to excellent yields from a common type of precursor.
- Zhou, Yujing,Zhang, Yan,Wang, Jianbo
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p. 10444 - 10453
(2016/11/18)
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- Borosilicate Activation of (Difluoroiodo)toluene in the gem-Difluorination of Phenyldiazoacetate Derivatives
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A combined experimental and computational investigation was conducted to identify a mild and effective Lewis-acidic activator for TolIF2in the gem-difluorination of diazo compounds. Computationally, borosilicate, a common constituent of laborat
- Sinclair, Geoffrey S.,Tran, Richard,Tao, Jason,Hopkins, W. Scott,Murphy, Graham K.
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supporting information
p. 4603 - 4606
(2016/09/28)
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- Diversity-oriented approach to CF3CHF-, CF3CFBr-, CF3CF2-, (CF3)2CH-, and CF3(SCF3)CH-substituted arenes from 1-(Diazo-2,2,2-trifluoroethyl)arenes
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Arenes substituted with perfluoroalkyl groups are attractive targets for drug and agrochemical development. Exploiting the carbenic character of donor/acceptor diazo compounds, a diversity-oriented synthesis of perfluoroalkylated arenes, for late stage fluorofunctionalization, is described. The reaction of 1-(diazo-2,2,2-trifluoroethyl)arenes with HF, F/Br, F2, CF3H, and CF3SH sources give direct access to a variety of perfluoroalkyl-substituted arenes presenting with incremental fluorine content. The value of this approach is also demonstrated for radiochemistry and positron emission tomography with the [18F]-labeling of CF3CHF-, CF3CBrF-, and CF3CF2-arenes from [18F]fluoride.
- Emer, Enrico,Twilton, Jack,Tredwell, Matthew,Calderwood, Samuel,Collier, Thomas Lee,Ligault, Benot,Taillefer, Marc,Gouverneur, Vronique
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p. 6004 - 6007
(2015/01/09)
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- Dihaloiodoarenes: α,α-dihalogenation of phenylacetate derivatives
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A hypervalent iodine reagent-based α-carbonyl dihalogenation reaction is reported. Treating diazoacetate derivatives with either iodobenzene dichloride or iodotoluene difluoride results in gem-dichlorination or gem-difluorination products, respectively. The reaction is catalyzed by either Lewis acid or Lewis base activation of the aryl-λ3-iodane (ArIX2) species and proceeds rapidly and chemoselectively to the desired gem-difunctionalized products in good to excellent yield.
- Tao, Jason,Tran, Richard,Murphy, Graham K.
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supporting information
p. 16312 - 16315
(2013/12/04)
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- Straightforward syntheses of hypervalent iodine(III) reagents mediated by selectfluor
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(Chemical Equation Presented) Use of Selectfluor allows hypervalent iodine(III) species such as aryl iodine(III) difluoride, diacetate, and di(trifluoroacetate) and Koser's salt to be easily prepared. Aryl iodine(III) difluoride and diacetate can be synthesized from the corresponding arene and elemental iodine in one-pot procedures.
- Ye, Chengfeng,Twamley, Brendan,Shreeve, Jean'ne M.
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p. 3961 - 3964
(2007/10/03)
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- Fluorinations of α-seleno carboxylic acid derivatives with hypervalent (difluoroiodo)toluene
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A very efficient synthesis of (difluoroiodo)toluene avoiding the use of elemental chlorine and elemental fluorine is described. We have fluorinated a series of α-acceptor substituted selenides using (difluoroiodo)toluene. The reactions are usually very clean and under the reaction conditions no further oxidized products are observed. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
- Arrica, Maria A.,Wirth, Thomas
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p. 395 - 403
(2007/10/03)
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- Fluorination of α-phenylsulfanyl esters using difluoroiodotoluene
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Treatment of α-phenylsulfanyl esters 11-14 with one equivalent of difluoroiodotoluene 3a produced the α-fluoro sulfides 17-20 in good overall yield through a Fluoro-Pummerer reaction. A second equivalent of reagent produced α,α-difluoro sulfides and a third led to α,α-difluoro sulfoxides. An identical pattern of reactivity was observed with the α-phenylsulfanyl lactone 26. This sequential fluorination-oxidation behaviour was exploited in the one-pot synthesis of 3-fluoro-2(5H)-furanone 33 starting from α-phenylsulfanylbutyrolactone 32.
- Motherwell, William B.,Greaney, Michael F.,Tocher, Derek A.
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p. 2809 - 2815
(2007/10/03)
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- A practical synthetic method of iodoarene difluorides without fluorine gas and mercury salts
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Iodoarene difluorides were synthesized in three steps from the corresponding iodoarenes without the use of dangerous reagents such as fluorine gas of harmful mercury salts.
- Sawaguchi, Masanori,Ayuba, Shinichi,Hara, Shoji
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p. 1802 - 1803
(2007/10/03)
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- Deiodinative fluorination of alkyl iodide with p-iodotoluene difluoride
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Oxidative fluorination of alkyl iodides with p-iodotoluene difluoride (4) was carried out. In the presence of Et3N-4HF, the fluorination reaction of prim-alkyl iodides selectively took place at the iodine position under mild conditions to give the corresponding alkyl fluorides in good yields.
- Sawaguchi, Masanori,Hara, Shoji,Nakamura, Yutaka,Ayuba, Shinichi,Fukuhara, Tsuyoshi,Yoneda, Norihiko
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p. 3315 - 3319
(2007/10/03)
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- Stereoselective synthesis of (E)-1-fluoro-1,3-enynes
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1-Fluoro-1,3-enynes were stereoselectively prepared by the cross-coupling reaction of 1-alkynes with β-fluoroalkenyliodides obtained from (β-fluoroalkenyl)iodonium salts. As the reaction proceeds under mild conditions, polyfunctionalized 1-fluoro-1,3-enyn
- Yoshida, Masanori,Yoshikawa, Shuhei,Fukuhara, Tsuyoshi,Yoneda, Norihiko,Hara, Shoji
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p. 7143 - 7148
(2007/10/03)
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- Regio- and stereoselective synthesis of fluoroalkadienes using β-fluoroalkenyliodonium salt
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(E,E)-δ-Fluoro-α,β,γ,δ-unsaturated carbonyl compounds and (3E)-4-fluoro-1,3-dienes were stereoselectively synthesized by the palladium-catalyzed coupling reaction of (2-fluoroalkenyl)(p-tolyl)iodonium fluorides with α,β-unsaturated carbonyl compounds and
- Yoshida,Nagahara,Fukuhara,Yoneda,Hara
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p. 2283 - 2288
(2007/10/03)
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- Fluorocyclization of unsaturated alcohols and carboxylic acids by iodotoluene difluoride and amine-HF complexes
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In the presence of amine-HF complexes, iodotoluene difluoride reacted with unsaturated alcohols and carboxylic acids to give cyclic fluoroethers and fluorolactones, respectively.
- Sawaguchi, Masanori,Hara, Shoji,Fukuhara, Tsuyoshi,Yoneda, Norihiko
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p. 277 - 280
(2007/10/03)
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- SYNTHESEN VON ARYLJOD(III)-DIFLUORIDEN DURCH DIREKTFLUORIERUNG VON ARYLJODIDEN
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The aryl iodides C6H5I, o-XC6H4I(X = F, I), m-FC6H4I and p-XC6H4I (X = F, Cl, Br, I, CH3, NO2) react with elemental fluorine at about -100 deg C in CCl3F to form the corresponding aryl iodine difluorides without attack on the aromatic ring.Preparations, (
- Naumann, D.,Ruether, G.
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p. 213 - 222
(2007/10/02)
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