- Facile synthesis of iodonium salts by reaction of organotrifluoroborates with p-iodotoluene difluoride
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A simple and easy method for the synthesis of various iodonium salts was developed, and involves the reaction of potassium organotrifluoroborates with p-iodotoluene difluoride under mild conditions. The one-pot synthesis of a (Z)-(2-fluoroalkenyl)iodonium
- Yoshida, Masanori,Osafune, Kanako,Hara, Shoji
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- The no-carrier-added synthesis of bromine-76 labeled alkenyl and alkynyl bromides using organotrifluoroborates
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A straightforward radiobromination procedure has been developed for the construction of radiobrominated alkenyl and alkynyl bromides. The organotrifluoroborates used as the reactive intermediates are unique in that they are quite polar and thus readily separated from the desired products. Copyright
- Kabalka, George W.,Mereddy, Arjun R.,Green, James F.
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- Stereoselective Suzuki-Miyaura cross-coupling reactions of potassium alkenyltrifluoroborates with alkenyl bromides
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The stereoselective synthesis of conjugated dienes using air-stable potassium alkenyltrifluoroborates as coupling partners is described. The palladium-catalyzed cross-coupling reaction of potassium (E)- and (Z)-alkenyltrifluoroborates with either (E)- or
- Molander, Gary A.,Felix, Luciana A.
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- Pd-Catalyzed coupling of benzyl bromides with BMIDA-substituted: N -tosylhydrazones: synthesis of trans -alkenyl MIDA boronates
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A palladium-catalyzed stereoselective synthesis of alkenyl boronates from N-methyliminodiacetyl boronate (BMIDA)-substituted N-tosylhydrazone and benzyl bromides is developed. A range of trans-alkenyl MIDA boronates as single stereoisomers were obtained in moderate yields with good functional group compatibility. The resultant boronate products may be transformed to other boron-containing compounds and may also be directly used in cross-coupling reactions.
- Li, Muyao,Li, Shichao,Li, Shu-Sen,Wang, Jianbo
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supporting information
p. 399 - 402
(2022/01/19)
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- Reaction rate differences between organotrifluoroborates and boronic acids in BINOL-catalyzed conjugate addition to enones
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Enantioselective organocatalysis has been successfully employed in combination with trifluoroborate reagents for novel organic transformations over the last decade. However, no experimental rate studies of these reactions have been reported. Herein we report Hammett plot analysis of the organocatalyzed enantioselective conjugate addition of alkenyl, aryl, and heteroaryl trifluoroborate salts to chalcone derivatives with substitution at both the β-aryl and keto-aryl positions. The rate trend for keto-aryl substitution diverges from that of boronic acid nucleophiles in that the keto-aryl substituent for trifluoroborate salts does not measurably impact reaction rate in a manner consistent with charge stabilization. In addition, variable temperature NMR in combination with quantitative thin-layer chromatography (TLC) analysis suggests that the reaction is impacted by the low solubility of the trifluoroborate salts, so particle size and stirring speed affect reaction rates.
- Brooks, Bailey,Hiller, Noemi,May, Jeremy A.
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supporting information
(2021/09/28)
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- Catalyst-free and solvent-free hydroboration of alkynes
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The hydroboration of alkynes with pinacolborane (HBpin) under catalyst- and solvent-free conditions was demonstrated. Various alkynes were smoothly converted into alkenyl boronate esters in good to excellent yields at 110 °C. The gram-scale hydroboration
- Jaladi, Ashok Kumar,Choi, Hyeon Seong,An, Duk Keun
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p. 13626 - 13632
(2020/09/07)
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- H2-Acceptorless Dehydrogenative Boration and Transfer Boration of Alkenes Enabled by Zirconium Catalyst
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The first example of an efficient and direct dehydrogenative boration of alkenes for vinyl boronate ester synthesis was achieved using a zirconium catalyst. Our methodology avoids using precious transition metals, additional hydrogen acceptors, high temperatures, and long reaction times, which were required to overcome the reducing ability of borane, to give alkyl boronate esters. Detailed mechanistic studies revealed a reversible reaction pathway and further suggested applying the zirconium complex as a “shuttle catalyst” for transfer boration, which thus sidesteps the use of relatively sensitive borane.
- Shi, Xiaonan,Li, Sida,Wu, Lipeng
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supporting information
p. 16167 - 16171
(2019/11/03)
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- Bifunctional Ligand Enables Efficient Gold-Catalyzed Hydroalkenylation of Propargylic Alcohol
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Using the previously designed biphenyl-2-ylphosphine ligand, featuring a remote tertiary amino group, the first gold-catalyzed intermolecular hydroalkenylation of alkynes has been developed. Synthetically valuable conjugated dienyl alcohols are formed in moderate to good yields. A range of alkenyltrifluoroborates are allowed as the alkenyl donor, and no erosion of alkene geometry and/or the propargylic configuration are detected. DFT calculations confirm the critical role of the remote basic group in the ligand as a general-base catalyst for promoting this novel gold catalysis with good efficiency.
- Liao, Shengrong,Porta, Alessio,Cheng, Xinpeng,Ma, Xu,Zanoni, Giuseppe,Zhang, Liming
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supporting information
p. 8250 - 8254
(2018/06/29)
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- A general method for interconversion of boronic acid protecting groups: Trifluoroborates as common intermediates
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We have developed a general protocol for the interconversion of diverse protected boronic acids, via intermediate organotrifluoroborates. N-Methyliminodiacetyl boronates, which have been hitherto resistant to direct conversion to trifluoroborates, have been shown to undergo fluorolysis at elevated temperatures. Subsequent solvolysis of organotrifluoroborates in the presence of trimethylsilyl chloride and a wide range of bis-nucleophiles enables the generation of a variety of protected boronic acids.
- Churches, Quentin I.,Hooper, Joel F.,Hutton, Craig A.
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p. 5428 - 5435
(2015/06/16)
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- Highly enantioselective Rh-Catalyzed Alkenylation of imines: Synthesis of Chiral Allylic Amines via Asymmetric addition of Potassium Alkenyltrifluoroborates to N-Tosyl imines
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For the first time, simple N-tosyl aryl aldimines, prepared from the condensation of tosyl amide and aromatic aldehydes, can be used as substrates in the rhodium catalyzed 1,2- addition reaction using alkenylboron nucleophiles. In the presence of 1.5 mol % of [RhCl(1e)]2, enantioselective addition of various potassium alkenyltrifluoroborates to aryl aldimines furnished the corresponding chiral allylic amines in 73-96% yield and 72->99.5% ee. Notably, this method efficiently provides the di-, tri-, and tetrasubstituted allylic N-tosyl amines with high asymmetric induction.
- Gopula, Balraj,Chiang, Chien-Wei,Lee, Way-Zen,Kuo, Ting-Shen,Wu, Ping-Yu,Henschke, Julian P.,Wu, Hsyueh-Liang
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supporting information
p. 632 - 635
(2014/04/03)
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- Preparation of organotrifluoroborate salts: Precipitation-driven equilibrium under non-etching conditions
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Simple, rapid, and scaleable: In contrast to current procedures using corrosive HF/MF or MHF2 reagents (M=e.g. K), a wide range of trifluoroborates can be rapidly, simply, and safely prepared from MF (M=K, Cs), RCO2H, and a boronic a
- Lennox, Alastair J. J.,Lloyd-Jones, Guy C.
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supporting information
p. 9385 - 9388
(2012/10/29)
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- Oxidative nucleophilic substitution: Transformation of alkylboronic derivatives
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An efficient amidation reaction is described in this paper. Potassium alkyltrifluoroborate salts can be transforming to amides from nitriles in the presence of copper acetate and boron trifluoride. An extension of this reaction allowed the formation of amines, ethers, and C-C bond.
- Cazorla, Clément,Métay, Estelle,Lemaire, Marc
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experimental part
p. 8615 - 8621
(2011/11/30)
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- Lewis acid-promoted friedel-crafts alkylation reactions with α-ketophosphate electrophiles
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The BF3·OEt2-promoted nucleophilic substitution of α-aryl-α-ketophosphates to afford α,α-diaryl ketone products is described. Electron-rich α-ketophosphates perform best, with electron-neutral and electron-poor substrates also tolerated. The reaction is tolerant of a range of aromatic, heteroaromatic, and nonaromatic nucleophiles, with yields ranging from 44% to 84%. Enantioenriched starting material yields racemic product, suggesting an SN1 pathway via an acylcarbenium ion.
- Smith, Austin G.,Johnson, Jeffrey S.
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supporting information; experimental part
p. 1784 - 1787
(2010/09/05)
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- Palladium-catalyzed oxidative homocoupling of potassium alkenyltrifluoroborates: synthesis of symmetrical 1,3-dienes
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Herein, we describe a convenient method for the synthesis of symmetrical 1,3-dienes employing an oxidative palladium-catalyzed homocoupling of potassium alkenyltrifluoroborates providing products in good yields relative to existing methodologies. This is the first report of a cross-dimerization of potassium alkenyltrifluoroborates.
- Weber, Minéia,Singh, Fateh V.,Vieira, Adriano S.,Stefani, Hélio A.,Paix?o, Marcio W.
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experimental part
p. 4324 - 4327
(2009/10/26)
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- Suzuki-Miyaura cross-coupling reactions of potassium alkenyltrifluoroborates
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We have previously reported that the palladium-catalyzed cross-coupling reaction of air-stable potassium alkenyltrifluoroborates with aryl halides and triflates proceeds readily with good yields. Recent progress in outlining the scope and limitations of s
- Molander, Gary A.,Bernardi, Carmem R.
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p. 8424 - 8429
(2007/10/03)
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- Potassium organotrifluoroborates: New partners in palladium-catalysed cross-coupling reactions
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The preparation of various potassium organotrifluoroborates bearing either aryl, alkenyl, or alkynyl substituents is described. These stable salts are shown to be very efficient partners in palladium-catalysed cross- coupling reactions with arenediazonium salts, affording biaryl and styrene derivatives in high yields.
- Darses, Sylvain,Michaud, Guillaume,Genet, Jean-Pierre
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p. 1875 - 1883
(2007/10/03)
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