The Chemical Record, Journal Year: 2023, Volume and Issue: 23(11)
Published: June 26, 2023
Abstract Due to their high versatility borylated and silylated compounds are inevitable synthons for organic chemists. To escape the classical hydroboration/hydrosilylation paradigm, chemists turned attention more modern green methods such as photoredox chemistry electrosynthesis. This account focuses on novel generation of boryl silyl radicals forge C−B C−Si bonds from our group.
Language: Английский
Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)
Published: Dec. 2, 2023
We report a combination of electrocatalysis and photoredox catalysis to perform selective C(sp3)-H arylation/alkylation alkanes, in which binary catalytic system based on earth-abundant iron nickel is applied. Reaction selectivity between two-component arylation three-component alkylation tuned by modulating the applied current light source. Importantly, an ultra-low anodic potential (~0.23 V vs. Ag/AgCl) this protocol, thus enabling compatibility with variety functional groups (>70 examples). The robustness method further demonstrated preparative scale late-stage diversification natural products pharmaceutical derivatives.
Language: Английский
Citations
31
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)
Published: Dec. 8, 2023
Abstract The development of boron reagents is crucial for synthetic chemistry. Herein, we present a scalable and practical synthesis diborodichloromethane (DBDCM) through the reaction trichloromethyllithium with bis(pinacolato)diboron (B 2 pin ). resulting DBDCM reagent serves as basic unit construction various structurally diverse gem ‐diborylalkanes controllable C−Cl functionalizations. Moreover, have developed consecutive tetra‐functionalizations tertiary quaternary carbon containing molecules. use isotopically enriched 13 C‐chloroform 10 B enables C‐DBDCM B‐DBDCM reagents, which are beneficial convenient carbon‐13 boron‐10
Language: Английский
Citations
26
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: May 2, 2024
The enormous and widespread use of organoboronic acids has prompted the development innovative synthetic methodologies to meet demands on structural diversity functional group tolerance. existing photoinduced defunctionalization radical borylation, typically focused conversion one C-X bond (X= Br, I, or other leaving group) into only C-B bond. Herein, we disclose a divergent dechloroborylation reaction enabled by dinuclear gold catalysis with visible light irradiation. A wide range structurally diverse alkyl boronic, α-chloroboronic, gem-diboronic esters can be synthesized in moderate good yields (up 92%). Its robustness is further demonstrated preparative scale applied late-stage diversification complex molecules. process hinges C-Cl relay activation readily available gem-dichloroalkanes through inner-sphere electron transfer, overcoming redox potential limits unreactive chlorides.
Language: Английский
Citations
15
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: June 19, 2024
Abstract The simultaneous activation of reactants on the anode and cathode via paired electrocatalysis has not been extensively demonstrated. This report presents a oxidative reductive catalysis based earth-abundant iron/nickel cocatalyzed C–C functionalization ubiquitous alcohols. A variety alcohols (i.e., primary, secondary, tertiary, or unstrained cyclic alcohols) can be activated at very low oxidation potential (~0.30 V vs. Ag/AgCl) photoelectrocatalysis coupled with versatile electrophiles. reactivity yields wide range structurally diverse molecules broad functional group compatibility (more than 50 examples).
Language: Английский
Citations
13
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(4)
Published: Dec. 8, 2023
Abstract General methods for the preparation of geminal bis(boronates) are great interest due to their widespread applications in organic synthesis. While terminal gem ‐diboron compounds readily accessible, construction sterically encumbered, internal analogues has remained a prominent challenge. Herein, we report formal umpolung strategy access these valuable building blocks. The available 1,1‐diborylalkanes were first converted into corresponding α‐halogenated derivatives, which then serve as electrophilic components, undergoing substitution with diverse array nucleophiles form series C−C, C−O, C−S, and C−N bonds. This protocol features good tolerance steric hindrance wide variety functional groups heterocycles. Notably, this can also be extended synthesis diaryl compounds, therefore providing general approach various types bis(boronates).
Language: Английский
Citations
21
Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(13), P. 3361 - 3377
Published: Jan. 1, 2023
This review highlights the recent advances in both electrochemical borylation and hydroboration to synthesize organoboron compounds transformation of construct carbon–carbon carbon–heteroatom bonds.
Language: Английский
Citations
13
Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(12), P. 3485 - 3490
Published: Jan. 1, 2024
Herein, we report electrochemically mediated trifluoromethylallene synthesis via the rearrangement of trifluoromethyl-containing 1,3-enynes under action silicon or boron radicals, with good selectivity and without external oxidants.
Language: Английский
Citations
5
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)
Published: May 31, 2024
Abstract gem ‐Diborylalkanes are highly valuable building blocks in organic synthesis and pharmaceutical chemistry due to their ability participate multi‐step cross‐coupling transformations, allowing for the rapid generation of molecular complexity. While progress has been made synthetic metholodology, construction β‐tertiary C(sp 3 )‐rich ‐diborylalkanes remains a challenge substrate limitations steric hindrance issues. An approach is presented that utilizes synergistic photoredox copper catalysis achieve efficient )−C(sp ) alkyl N ‐hydroxyphthalimide esters, which can easily be obtained from carboxylic acids, with diborylmethyl species, providing series 1°, 2°, even 3° β positions. Furthermore, this also applied complex medicinal compounds natural products, offering access complexity late‐stage functionalization drug candidates. Mechanistic experiments revealed Cu(I) species participated both process key bond‐forming step.
Language: Английский
Citations
5
Organic Letters, Journal Year: 2024, Volume and Issue: 26(25), P. 5341 - 5346
Published: June 14, 2024
An unprecedented VCP-CP (vinylcyclopropane-cyclopentene) rearrangement approach has been established herein by virtue of the pyridine-boronyl radical catalyzed intramolecular ring expansions. This metal-free pathway harnesses readily available catalysts and unactivated vinylcyclopropane starting materials, providing an array cyclopentene derivatives chemoselectively under relatively mild conditions. Mechanistic studies support idea that boronyl engages in generation allylic/ketyl species, thus inducing opening cyclopropanes following cyclization processes.
Language: Английский
Citations
5
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)
Published: July 3, 2024
Enantioselective transformation of ubiquitous C(sp
Language: Английский
Citations
5