Tandem Synthesis of 9,10‐Dihydro‐9,10‐diboraanthracenes via Elusive <i>ortho</i>‐Lithiated Phenylboronates

Luliński, Sergiusz; Smętek, Jaromir; Durka, Krzysztof; Serwatowski, Janusz

doi:10.1002/ejoc.201300868

Cited by 27 publications

(23 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Starting materials including various benzene derivatives, Me 2 (H)SiCl, B(OMe) 3 were used as received without further purification. The syntheses of 1a, [13] 1c, [14] 1d, [15] 2a [16] and 2b [17] were reported previously. 1 H and 13 C NMR chemical shifts are given relative to TMS by using residual solvent resonances.…”

Section: Methodsmentioning

confidence: 99%

“…11 B, 19 F and 29 Si NMR chemical shifts are given relative to BF 3 ·Et 2 O, CFCl 3 and TMS, respectively. The syntheses of 1a, [13] 1c, [14] 1d, [15] 2a [16] and 2b [17] were reported previously. However, published procedures lack experimental and analytical details and therefore we have decided to include complete synthetic protocols and characterization for the mentioned compounds.…”

Section: Methodsmentioning

confidence: 99%

“…8 g (95 %) 1 H NMR (400 MHz, CDCl 3 ): δ = 7.43 (t, J = 7.9 Hz, 1 H), 7.29 (dd, J = 8.2, 1.7 Hz, 1 H), 7.23 (dd, J = 9.6, 1.7 Hz, 1 H), 5.54 (s, 1 H),3.34 (s, 6 H) ppm 13. C 43.40, H 4.05; found C 43.15, H 4.14.1-Bromo-3-(dimethoxymethyl)-5-fluorobenzene (2b):[17] This compound, b.p. 19 F NMR (376 MHz, CDCl 3 ): δ = -116.54 (m) ppm.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and Transformations of Functionalized Benzosiloxaboroles

et al. 2017

Self Cite

View full text Add to dashboard Cite

The synthesis and characterization of a series of fluorinated benzosiloxaboroles bearing synthetically useful formyl and cyano groups is reported. These compounds have been obtained by multistep syntheses starting with simple halogenated benzenes. The general synthetic protocol was based on the generation of ortho‐boronated aryldimethylsilanes which undergo dehydrogenative cyclization upon hydrolytic workup due to activation of the Si–H bond by the adjacent boronic group. In some cases the synergy of adjacent boron‐ and silicon‐based functionalities resulted in an unexpected hydrosilylation of the CHO group under mild aqueous conditions. The reduction of a benzosiloxaborole derivative bearing the formyl group at the ortho position with respect to the boron atom resulted in a structural transformation reflecting the higher stability of the carboxaborole heterocycle with respect to its silicon counterpart. Thus, a unique heterocyclic system featuring a central 10‐membered ring comprising two borasiloxane linkages was isolated.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis and Transformations of Functionalized Benzosiloxaboroles

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…Luliński, Durka et al. have published a synthesis of 16 through treatment of 11 with 4 equivalents of t BuLi (THF, −80 °C; 33 %) . In our hands, this protocol gave negligible yields.…”

Section: Resultsmentioning

confidence: 99%

C‐Halogenated 9,10‐Diboraanthracenes: How the Halogen Load and Distribution Influences Key Optoelectronic Properties

Brend'amour

Gilmer

Bolte

et al. 2018

Chemistry A European J

View full text Add to dashboard Cite

9,10‐Dihydro‐9,10‐diboraanthracenes (DBAs) have low‐energy LUMOs and narrow HOMO–LUMO gaps and are thus attractive electron‐transporting and light‐emitting materials in optoelectronic devices. A systematic series of ten C‐halogenated 9,10‐(Mes)2‐DBAs was synthesized and studied by cyclic voltammetry, UV/Vis absorption and emission spectroscopy, and quantum‐chemical calculations (Mes=mesityl). We probed the influence of the nature of the halogen atoms and the halogen substitution patterns on key optoelectronic properties of the DBAs. All 9,10‐(Mes)2 derivatives can be reversibly reduced at the DBA cores and at electrode potentials between E1/2Red1=−1.84 and −1.26 V (vs. FcH/FcH+). The most bathochromic UV/Vis absorption and the fluorescence emission of each DBA correspond to an ICT transition between the Mes rings and the DBA core. Br substituents lower the DBA LUMO energy and narrow the energy gap to the highest degree along the series F

show abstract

“…In the presence of CO 2 ligands, the calculations were performed by using n ‐hexane as solvent. Such an approach was successfully applied in our previous studies on the mechanism of HLE in selected haloarenes 63,69…”

Section: Methodsmentioning

confidence: 99%

Is Carbon Dioxide Able to Activate Halogen/Lithium Exchange?

et al. 2014

Self Cite

View full text Add to dashboard Cite

The unexpected effect of carbon dioxide on halogen–lithium exchange (HLE) reactions of selected haloarenes with tBuLi was investigated. In an aliphatic hydrocarbon solvent (pentane), the HLE does not occur at ca. –70 °C but, surprisingly, pouring the mixture of reactants onto dry ice and subsequent aqueous acidic hydrolysis gave carboxylic acids resulting from the quench of the first‐formed aryllithiums with carbon dioxide. This suggests that CO2 acts as a promoter of the HLE and, subsequently, serves as an electrophile to trap the aryllithium intermediates that are generated in situ. Theoretical DFT calculations were used to develop a plausible mechanism for the reaction, which indicates that CO2 is a much weaker donor than tetrahydrofuran (THF) so the cleavage of inert tBuLi cubic tetramers into more reactive solvated dimeric species (tBuLi)2(CO2)4 is disfavored by 42.8 kJ per mol of (tBuLi)4. It is possible that this deaggregation process occurs to some extent when a large excess of CO2 is used.

show abstract

Tandem Synthesis of 9,10‐Dihydro‐9,10‐diboraanthracenes via Elusive ortho‐Lithiated Phenylboronates

Cited by 27 publications

References 41 publications

Synthesis and Transformations of Functionalized Benzosiloxaboroles

Synthesis and Transformations of Functionalized Benzosiloxaboroles

C‐Halogenated 9,10‐Diboraanthracenes: How the Halogen Load and Distribution Influences Key Optoelectronic Properties

Is Carbon Dioxide Able to Activate Halogen/Lithium Exchange?

Contact Info

Product

Resources

About