7.24 Oxidation of Carbon–Halogen Bonds

Itoh, Akichika; Miura, Tsuyoshi; Tada, Norio

doi:10.1016/b978-0-08-097742-3.00728-x

Cited by 6 publications

(7 citation statements)

References 209 publications

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“…In order to initiate Kornblum reaction between DMSO and BBr, temperatures of 70−80°C and 100−110°C are required for converting the BBr to benzaldehyde and obtaining HBr, as shown in Scheme 1a. 60 The c-PbI 2 absorption curve, which can be seen in Figure 4d, shows the removal of Pb-DMSO complexes versus an applied temperature after BBr washing. As the temperature increases, not only the intensity of absorption increases, but also the DMSO complexes with PbI 2 disappear.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…As shown in Figure d, the Pb-DMSO complexes are removed from the structure only when the temperatures between 80 ° C and 100 ° C are applied. In order to initiate Kornblum reaction between DMSO and BBr, temperatures of 70–80 ° C and 100–110 ° C are required for converting the BBr to benzaldehyde and obtaining HBr, as shown in Scheme a . The c-PbI 2 absorption curve, which can be seen in Figure d, shows the removal of Pb-DMSO complexes versus an applied temperature after BBr washing.…”

Section: Results and Discussionmentioning

confidence: 99%

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Approach To Enhance the Stability and Efficiency of Triple-Cation Perovskite Solar Cells by Reactive Antisolvents

Mutlu

Yeşil

Kıymaz

et al. 2020

ACS Appl. Energy Mater.

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Controlling thin-film crystallization kinetics of perovskites is vital for the fabrication of highly efficient and stable perovskite solar cells (PSCs). Because of the low solubility of lead halogen derivatives in dimethylformamide solvent and poor film quality, addition of dimethylsulfoxide (DMSO) to the solution as a cosolvent has a great effect on the crystallization kinetics and morphology of perovskite thin films. However, Pb-DMSO and residual DMSO complexes that are difficult to be removed from the structure can lead to structural deformations and stability issues. Here, two different reagents such as benzyl chloride (BCl) and benzyl bromide (BBr) are applied as antisolvents to eliminate these problems utilizing the Kornblum oxidation reactions in the triple-cation perovskite thin films formed by the one-step coating method. Electrochemical impedance spectroscopy (EIS) analysis has been carried out to explain the charge transfer resistances and capacitive behaviors under illuminated conditions. EIS measurements show that washing with BBr antisolvent reduces the charge recombination in PSCs and leads to the best device performance with improved charge transport, yielding a 19.2% power conversion efficiency with a higher open circuit voltage (V oc ) of 1100 mV compared to washing with chlorobenzene (CB) and BCl. Resistances at the low-frequency region in Nyquist complex plots associated with charge recombination resistances were measured to be 1430, 564, and 3000 ohm, which are in good agreement with short circuit currents 23.3, 23.1, and 24.8 mA/cm 2 for devices fabricated with CB, BCl, and BBr, respectively. Removal of the residual DMSO and Pb-DMSO complexes via washing with BBr results in achieving more stable and highly efficient solar cells, which maintained 94% of the initial efficiency after 1 month.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Approach To Enhance the Stability and Efficiency of Triple-Cation Perovskite Solar Cells by Reactive Antisolvents

Mutlu

Yeşil

Kıymaz

et al. 2020

ACS Appl. Energy Mater.

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“…DMSO and amine oxide oxidation of alkyl iodides and tosylates has not been employed in bond-forming cascades . The cyclization cascade of iodide 10a (Scheme ) requires precise timing for the oxidation ( 10a → 11a → 13 ) and cyclization steps ( 13a′ → 14a or 13a′′ → 14b ) because a slow deprotonation of the sulfonium salt 11a incurs the potential for a premature cyclization of the nucleophilic enol ether to afford decalone 12 ; early oxidative explorations in DMSO with 10a and amine oxide protocols afforded only decalone 12 .…”

Section: Resultsmentioning

confidence: 99%

Oxidative DMSO Cyclization Cascade to Bicyclic Hydroxyketonitriles

et al. 2022

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Thermolysis of ω-iodoalkyl-β-siloxyalkenenitriles in DMSO triggers an oxidative cyclization cascade that affords highly oxygenated hydrindanones, decalones, and undecanones. The cyclization cascade is highly unusual on three counts: the cyclization installs a contiguous array of tertiary–quaternary–tertiary centers, thermolysis equilibrates a quaternary center, and the enolsilyl ether crossed-aldol proceeds without a catalyst.

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“…This behavior is common to many other substituted benzyl halides resulting in a transformation also known as the Hass-Bender oxidation. [54] Conversely, the same reaction carried out on 4-nitrobenzyl bromide affords the corresponding C-alkylated product 89 in 83% yield with the presence of only 1% of the corresponding 4-nitrobenzaldehyde.…”

Section: Early Studiesmentioning

confidence: 92%

Synthetic Approaches to the Challenging Direct C‐Alkylation and C‐Allylation of Unactivated Nitroalkanes

Palmieri,

Petrini

2023

Adv Synth Catal

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The limited nucleophilic character and the bidentate nature of unactivated nitroalkane anions (nitronates) makes the corresponding alkylation and allylation procedures rather troublesome. This aspect is in sharp contrast with other commonly employed processes involving nitronate anions such as conjugate additions or nitroaldol reactions. This review summarizes the most rewarding approaches that along the years have been devised to overcome this limitation. Efficient methods are nowadays based on metal‐catalyzed processes involving purely ionic or mixed ionic‐radical intermediates including photoenzymatic reactions.

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7.24 Oxidation of Carbon–Halogen Bonds

Cited by 6 publications

References 209 publications

Approach To Enhance the Stability and Efficiency of Triple-Cation Perovskite Solar Cells by Reactive Antisolvents

Approach To Enhance the Stability and Efficiency of Triple-Cation Perovskite Solar Cells by Reactive Antisolvents

Oxidative DMSO Cyclization Cascade to Bicyclic Hydroxyketonitriles

Synthetic Approaches to the Challenging Direct C‐Alkylation and C‐Allylation of Unactivated Nitroalkanes

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