Reactions of CF3-substituted boranes with α-diazocarbonyl compounds

Elkin, Pavel K.; Levin, Vitalij V.; Dilman, Alexander D.; Стручкова, Марина И.; Belyakov, Pavel A.; Arkhipov, Dmitry E.; Korlyukov, Alexander A.; Tartakovsky, Vladimir A.

doi:10.1016/j.tetlet.2011.07.141

Cited by 29 publications

(17 citation statements)

References 28 publications

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“…Figure 1 b shows that Li + is coordinated to a catechol oxygen and to three THF molecules. [11,12] The kinetics of the reactions of the BACs 3-4 and 8-14 with the benzhydrylium ions 15 a-d were monitored by timeresolved UV/Vis spectroscopy in CH 3 CN at the l max of 15 (Table 1). [11,12] The kinetics of the reactions of the BACs 3-4 and 8-14 with the benzhydrylium ions 15 a-d were monitored by timeresolved UV/Vis spectroscopy in CH 3 CN at the l max of 15 (Table 1).…”

Section: Scheme 1 Reactions Of Boron Ate Complexes (Bacs) With Electmentioning

confidence: 99%

“…[10] The quaternary boron atoms in both BACs have perfect tetrahedral environments (tetrahedral character > 99.9 %). [11,12] The kinetics of the reactions of the BACs 3-4 and 8-14 with the benzhydrylium ions 15 a-d were monitored by timeresolved UV/Vis spectroscopy in CH 3 CN at the l max of 15 (Table 1). In the presence of more than ten equivalents of the BACs, monoexponential decays of the benzhydrylium ions absorbances were observed, indicating pseudo-first-order kinetics.…”

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confidence: 99%

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Fine‐Tuning the Nucleophilic Reactivities of Boron Ate Complexes Derived from Aryl and Heteroaryl Boronic Esters

et al. 2015

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Boron ate complexes derived from thienyl and furyl boronic esters and aryllithium compounds have been isolated and characterized by X-ray crystallography. Products and mechanisms of their reactions with carbenium and iminium ions have been analyzed. Kinetics of these reactions were monitored by UV/Vis spectroscopy, and the influence of the aryl substituents, the diol ligands (pinacol, ethylene glycol, neopentyl glycol, catechol), and the counterions on the nucleophilic reactivity of the boron ate complexes were examined. A Hammett correlation confirmed the polar nature of their reactions with benzhydrylium ions, and the correlation lg k(20 °C)=sN (E+N) was employed to determine the nucleophilicities of the boron ate complexes and to compare them with those of other borates and boronates. The neopentyl and ethylene glycol derivatives were found to be 10(4) times more reactive than the pinacol and catechol derivatives.

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Section: Scheme 1 Reactions Of Boron Ate Complexes (Bacs) With Electmentioning

confidence: 99%

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confidence: 99%

Fine‐Tuning the Nucleophilic Reactivities of Boron Ate Complexes Derived from Aryl and Heteroaryl Boronic Esters

et al. 2015

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“…line state, [14] only two heteroatoms in the pinBCF 2 H unit of coordinate on the K + (18-crown-6) ion. One of the oxygen atoms in the 5-membered ring (O1) coordinates on the potassium ion, and correspondingly the B1À O1 distance is elongated compared with the B1À O2 bond.…”

Section: Full Papermentioning

confidence: 99%

Convenient Preparation and Structure Determination of Air‐ and Moisture‐Tolerant Difluoromethylborates

Yokawa

Ito

2020

Chemistry An Asian Journal

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Convenient and reliable synthetic methods for difluoromethylborates have been established. The intermediary generated difluoromethylsilicate species from TMSCF 2 H (TMS = trimethylsilyl) and potassium tert-butoxide were allowed to react with pinBPh (Me 4 C 2 O 2 BPh) in the presence of 18-crown-6 to give the corresponding borate compound [pinB(Ph)CF 2 H] À K + (18-crown-6) as an air-and moisture-tolerant solid. The unambiguously determined crystal structure of [pinB(Ph)CF 2 H] À K + (18-crown-6) revealed that the difluoromethylborate unit partially coordinated on the potassium ion. Reaction of [pinB(Ph)CF 2 H]-K + (18-crown-6) with potassium difluoride (KHF 2) in acetic acid enabled substitution of the pinacol unit and phenyl group with fluorides, and gave (difluoromethyl)trifluoroborate [F 3 BCF 2 H]-K + (18-crown-6) in a good yield. The crystal structure of air-and moisturetolerant [F 3 BCF 2 H]-K + (18-crown-6), which would be a promising reagent for synthesis of various difluoromethylboron species, showed a polyrotaxane-like polymeric structure based on the K•••F interactions between the K + (18-crown-6), CF 2 H, and BF 3 units.

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“…40 Stable potassium alkyl, aryl, alkenyl and alkynyltrifluoromethyldimethoxy boronates 50 react with TMSCl and α-diazocarbonyl compounds to give similar products 51 (Scheme 18). 41 This journal is © The Royal Society of Chemistry 2014 Using 2,2,2-trifluorodiazoethane, Molander et al have been able to isolate the bench-stable α-trifluoromethylated potassium trifluoroborates 52 or pinacolboronates 53 which result from the addition of RBF 3 K reagents (R = alkyl, alkynyl, alkenyl and (het)aryl) in the presence of TMSCl or (p-tolyl)SiCl 3 (Scheme 19). 42 These compounds were amenable to classical C-B fuctionalization reactions such as protodeboronation, thus providing a good method for trifluoroethylation (eg., 54).…”

Section: Reactions With α α α α-Diazocarbonyl Compounds and Tosylhydrmentioning

confidence: 99%

Transition-metal-free C–C bond forming reactions of aryl, alkenyl and alkynylboronic acids and their derivatives

2014

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Investigation of new methods for the synthesis of C-C bonds is fundamental for the development of new organic drugs and materials. Aryl-, alkenyl- and alkynylboronic acids and their derivatives constitute attractive reagents towards this end, due to their stability, low toxicity and ease of handling. However, these compounds are only moderately nucleophilic. Consequently, the most popular C-C bond forming reactions of these boronic acids, such as the Suzuki-Miyaura, Heck, and Hayashi-Miyaura reactions, or additions to C=O and C=N bonds, require catalysis by transition metals. However, due to the toxicity and cost of transition metals, some new methods for C-C bond formation using aryl-, alkenyl- and alkynylboronic acids under transition-metal-free conditions are beginning to emerge. In this tutorial review, the recent synthetic advances in this field are highlighted and discussed.

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Reactions of CF3-substituted boranes with α-diazocarbonyl compounds

Cited by 29 publications

References 28 publications

Fine‐Tuning the Nucleophilic Reactivities of Boron Ate Complexes Derived from Aryl and Heteroaryl Boronic Esters

Fine‐Tuning the Nucleophilic Reactivities of Boron Ate Complexes Derived from Aryl and Heteroaryl Boronic Esters

Convenient Preparation and Structure Determination of Air‐ and Moisture‐Tolerant Difluoromethylborates

Transition-metal-free C–C bond forming reactions of aryl, alkenyl and alkynylboronic acids and their derivatives

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