Synthesis of α-Chloroboronic Esters via Photoredox-Catalyzed Chloro-Alkoxycarbonylation of Vinyl Boronic Esters DOI
Wen‐Duo Li, Nana Wei, Nan Feng

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 9, 2025

α-Chloroboronic esters are a class of stable multifunctional molecules that show unique applications in pharmaceutical science and organic chemistry. Despite their apparent utility, the synthetic methods these compounds remain limited. Herein, novel strategy for efficient synthesis α-chloroboronic is developed via photoredox-catalyzed chloro-alkoxycarbonylation vinyl boronic esters. This features advantages high atom economy, environmental friendliness, excellent functional group compatibility was verified by cross-coupling variety free alcohols, oxalyl chlorides, Control experiments mechanistic studies indicate alkoxycarbonyl radical α-boryl carbocation key intermediates this transformation.

Language: Английский

Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions DOI Creative Commons
Xiaoming Ma, Qiang Zhang, Wei Zhang

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(7), P. 3027 - 3027

Published: March 28, 2023

Radical transformations are powerful in organic synthesis for the construction of molecular scaffolds and introduction functional groups. In radical difunctionalization reactions, radicals first functionalized intermediates can be relocated through resonance, hydrogen atom or group transfer, ring opening. The resulting undertake following paths second functionalization: (1) couple with other groups, (2) oxidize to cations then react nucleophiles, (3) reduce anions electrophiles, (4) metal-complexes. rearrangements provide opportunity 1,3-, 1,4-, 1,5-, 1,6-, 1,7-difunctionalization products. Multiple ways initiate reaction coupling intermediate make reactions good at remote positions. These offer advantages synthetic efficiency, operation simplicity, product diversity.

Language: Английский

Citations

21
Photocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanes DOI Creative Commons

Degong Kong,

Muliang Zhang, Yuchao Zhang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 2, 2023

Geminal and vicinal borosilanes are useful building blocks in synthetic chemistry material science. Hydrosilylation/hydroborylation of unsaturated systems offer expedient access to these motifs. In contrast the well-established transition-metal-catalyzed methods, radical approaches rarely explored. Herein we report synthesis geminal from α-selective hydrosilylation alkenyl boronates via photoinduced hydrogen atom transfer (HAT) catalysis. Mechanistic studies implicate that α-selectivity originates a kinetically favored addition an energetically HAT process. We further demonstrate selective through allyl 1,2-boron migration. These strategies exhibit broad scopes across primary, secondary, tertiary silanes various boron compounds. The utility is evidenced by multi-borosilanes diverse fashion scaling up continuous-flow synthesis.

Language: Английский

Citations

21
Direct Light‐Enabled Access to α‐Boryl Radicals: Application in the Stereodivergent Synthesis of Allyl Boronic Esters** DOI Creative Commons

Alessandro Marotta,

Fang Hao,

Callum E. Adams

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: June 16, 2023

Abstract Operationally simple strategies to assemble boron containing organic frameworks are highly enabling in synthesis. While conventional retrosynthetic logic has engendered many platforms focusing on the direct formation of C−B bonds, α‐boryl radicals have recently reemerged as versatile open‐shell alternatives access organoborons via adjacent C−C bond formation. Direct light‐enabled α‐activation is currently contingent photo‐ or transition metal‐catalysis activation efficiently generate radical species. Here, we disclose a facile α‐halo boronic esters using only visible light and Lewis base enable homolytic scission. Intermolecular addition styrenes facilitates rapid construction E ‐allylic esters. The simplicity permits strategic merger this construct with selective energy transfer catalysis complimentary stereodivergent synthesis Z

Language: Английский

Citations

21
Ate complexes in organic synthesis: From ate reagents to ate catalysts DOI Creative Commons
Yang’en You, Congcong Yin,

Liren Xu

et al.

Green Synthesis and Catalysis, Journal Year: 2024, Volume and Issue: 5(3), P. 141 - 152

Published: May 8, 2024

The realm of application organometallic catalysis to organic synthesis has witnessed a transformative shift in recent years, owing much the evolution ate complexes from mere reagents versatile catalysts. Ate complexes, formed through coordination neutral Lewis acid with an anionic base, have emerged as pivotal intermediates that not only facilitate transformations but also serve efficient catalysts wide range chemical reactions. This review presents fascinating journey highlighting their development stoichiometric active Historically, were primarily regarded species essential for various metal-catalyzed transformations. However, constant research unveiled potential own right, reshaping landscape modern synthesis. In this minireview, we discuss role synthesis, early days reactive current stature catalytic pioneers offering glimpse into exciting future dynamic field.

Language: Английский

Citations

8
Radical Addition Enables 1,2‐Aryl Migration from a Vinyl‐Substituted All‐Carbon Quaternary Center DOI
Zexian Li, Minyan Wang, Zhuangzhi Shi

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(1), P. 186 - 190

Published: Sept. 14, 2020

Abstract An efficient method for photocatalytic perfluoroalkylation of vinyl‐substituted all‐carbon quaternary centers involving 1,2‐aryl migration has been developed. The rearrangement reactions use fac ‐Ir(ppy) 3 , visible light and commercially available fluoroalkyl halides can generate valuable multisubstituted perfluoroalkylated compounds in a single step that would be challenging to prepare by other methods. Mechanistically, the photoinduced alkyl radical addition an alkene leads vicinal aryl substituent from its adjacent center with concomitant generation C‐radical bearing two electron‐withdrawing groups is further reduced hydrogen donor complete domino sequence.

Language: Английский

Citations

50
Transition‐Metal‐Free Oxidative Cross‐Coupling of Tetraarylborates to Biaryls Using Organic Oxidants DOI Creative Commons

Carolin Gerleve,

Armido Studer

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(36), P. 15468 - 15473

Published: March 11, 2020

Abstract Readily prepared tetraarylborates undergo selective (cross)‐coupling through oxidation with Bobbitt's salt to give symmetric and unsymmetric biaryls. The organic oxoammonium can be used either as a stoichiometric oxidant or catalyst in combination situ generated NO 2 molecular oxygen the terminal oxidant. For selected cases, oxidative coupling is also possible /O without any additional nitroxide‐based cocatalyst. Transition‐metal‐free catalytic ligand cross‐coupling of unprecedented introduced method provides access various biaryl heterobiaryl systems.

Language: Английский

Citations

47
Transition metal-free synthesis of alkyl pinacol boronates DOI
Kanak Kanti Das,

Swagata Paul,

Santanu Panda

et al.

Organic & Biomolecular Chemistry, Journal Year: 2020, Volume and Issue: 18(44), P. 8939 - 8974

Published: Jan. 1, 2020

This review systematically outlined the research in area of transition metal free synthesis alkyl pinacol boronates, which are versatile and important scaffolds to construct diverse organic compounds.

Language: Английский

Citations

46
1,2‐Boryl Migration Enables Efficient Access to Versatile Functionalized Boronates DOI

Xia‐Min Jiang,

Xinru Liu, Ang Chen

et al.

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(9)

Published: Jan. 12, 2022

Abstract Organoboronates are synthetically useful and highly valuable building blocks in synthetic medicinal chemistry. Two‐electron reactions allow for the rapid construction of organoboronates via nucleophilic 1,2‐boron shift boron ate complexes or MIDA‐mediated 1,2‐boryl migration. Radical approaches through neutral boronic esters have been demonstrated to be feasible, providing complementary methods access these privileged scaffolds. In this Review, recent achievements highlighted future opportunities discussed, with an emphasis on different operative modes catalysis reaction pathways.

Language: Английский

Citations

26
Synthesis of 1,3‐Bis‐(boryl)alkanes through Boronic Ester Induced Consecutive Double 1,2‐Migration DOI Creative Commons
Cai You, Armido Studer

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(39), P. 17245 - 17249

Published: June 24, 2020

A general and efficient approach for the preparation of 1,3-bis-(boryl)alkanes is introduced. It shown that readily generated vinylboron ate complexes react with commercially available ICH

Language: Английский

Citations

39
Radical Aryl Migration from Boron to Carbon DOI Creative Commons
Dinghai Wang, Christian Mück‐Lichtenfeld, Constantin G. Daniliuc

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(25), P. 9320 - 9326

Published: June 20, 2021

Radical aryl migration reactions represent a unique type of organic transformations that involve the intramolecular an group from carbon or heteroatom to C- heteroatom-centered radical through spirocyclic intermediate. Various elements, including N, O, Si, P, S, Sn, Ge, and Se, have been reported participate in migrations. However, boron center has not date. In this communication, 1,5-aryl boronate complexes is presented. C-radicals readily generated addition onto alkenyl are shown engage provide 4-aryl-alkylboronic esters. As can be situ by reaction alkenylboronic acid esters with lithium reagents, moiety varied, providing access series arylated products starting same ester via divergent chemistry. Reactions proceed high diastereoselectivity under mild conditions, also analogous 1,4-aryl shifts feasible. The suggested mechanism supported DFT calculations.

Language: Английский

Citations

31