371-11-9Relevant articles and documents
A Practical, Large-Scale Synthesis of p -(Difluoroiodo)toluene (p -TolIF 2)
Murphy, Graham K.,Tao, Jason
, p. 3055 - 3059 (2019)
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
Fluorohydration of alkynes via I(I)/I(III) catalysis
Daniliuc, Constantin G.,Gilmour, Ryan,Neufeld, Jessica
supporting information, p. 1627 - 1635 (2020/09/11)
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.
Electrochemical Vicinal Difluorination of Alkenes: Scalable and Amenable to Electron-Rich Substrates
Doobary, Sayad,Sedikides, Alexi T.,Caldora, Henry P.,Poole, Darren L.,Lennox, Alastair J. J.
supporting information, p. 1155 - 1160 (2019/12/11)
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.
Photocatalytic Fluoro Sulfoximidations of Styrenes
Bolm, Carsten,Ma, Ding,Tu, Yongliang,Wang, Chenyang
, p. 14134 - 14137 (2020/06/17)
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
Hypervalent Iodine(III)-Catalyzed Balz–Schiemann Fluorination under Mild Conditions
Xing, Bo,Ni, Chuanfa,Hu, Jinbo
, p. 9896 - 9900 (2018/07/31)
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.
Deconstructing the Catalytic, Vicinal Difluorination of Alkenes: HF-Free Synthesis and Structural Study of p-TolIF2
Sarie, Jér?me C.,Thiehoff, Christian,Mudd, Richard J.,Daniliuc, Constantin G.,Kehr, Gerald,Gilmour, Ryan
, p. 11792 - 11798 (2017/11/24)
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)
Geminal difunctionalization of α-diazo arylmethylphosphonates: Synthesis of fluorinated phosphonates
Zhou, Yujing,Zhang, Yan,Wang, Jianbo
, p. 10444 - 10453 (2016/11/18)
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.
Borosilicate Activation of (Difluoroiodo)toluene in the gem-Difluorination of Phenyldiazoacetate Derivatives
Sinclair, Geoffrey S.,Tran, Richard,Tao, Jason,Hopkins, W. Scott,Murphy, Graham K.
supporting information, p. 4603 - 4606 (2016/09/28)
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
Diversity-oriented approach to CF3CHF-, CF3CFBr-, CF3CF2-, (CF3)2CH-, and CF3(SCF3)CH-substituted arenes from 1-(Diazo-2,2,2-trifluoroethyl)arenes
Emer, Enrico,Twilton, Jack,Tredwell, Matthew,Calderwood, Samuel,Collier, Thomas Lee,Ligault, Benot,Taillefer, Marc,Gouverneur, Vronique
, p. 6004 - 6007 (2015/01/09)
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.
Dihaloiodoarenes: α,α-dihalogenation of phenylacetate derivatives
Tao, Jason,Tran, Richard,Murphy, Graham K.
supporting information, p. 16312 - 16315 (2013/12/04)
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.
