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

Stereospecific 1,2‐Migrations of Boronate Complexes Induced by Electrophiles DOI Creative Commons
Hui Wang, Changcheng Jing, Adam Noble

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(39), P. 16859 - 16872

Published: June 27, 2020

The stereospecific 1,2-migration of boronate complexes is one the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals natural products. Typically, driven by displacement an α-leaving group, oxidation α-boryl radical, or electrophilic activation alkenyl complex. aim this article summarize recent advances rapidly expanding field electrophile-induced groups sp

Language: Английский

Citations

123
Radical‐Induced 1,2‐Migrations of Boron Ate Complexes DOI Creative Commons
Marvin Kischkewitz,

Florian W. Friese,

Armido Studer

et al.

Advanced Synthesis & Catalysis, Journal Year: 2019, Volume and Issue: 362(11), P. 2077 - 2087

Published: Dec. 24, 2019

Abstract 1,2‐Boron ate rearrangements represent a fundamental class of transformations to establish new C−C bonds while retaining the valuable boron moiety in product. In established ionic processes, complex is activated by an external electrophile induce 1,2‐migration from adjacent sp 3 or 2 carbon atom. Recently, two complementary radical polar crossover approaches have been explored for both classes, 1,2‐migrations and centers. This review describes general concepts this emerging research field summarizes recent developments radical‐induced carbon. magnified image

Language: Английский

Citations

78
Saturated Boronic Acids, Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry DOI
Dmitriy M. Volochnyuk, Alina O. Gorlova, Oleksandr O. Grygorenko

et al.

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(62), P. 15277 - 15326

Published: Sept. 9, 2021

Abstract This review discusses recent advances in the chemistry of saturated boronic acids, boronates, and trifluoroborates. Applications title compounds design boron‐containing drugs are surveyed, with special emphasis on α‐amino derivatives. A general overview as modern tools to construct C(sp 3 )−C )‐heteroatom bonds is given, including developments Suzuki‐Miyaura Chan‐Lam cross‐couplings, single‐electron‐transfer processes metallo‐ organocatalytic photoredox reactions, transformations boron “ate” complexes. Finally, an attempt summarize current state art synthesis trifluoroborates made, a brief mention “classical” methods (transmetallation organolithium/magnesium reagents species, anti‐Markovnikov hydroboration alkenes, modification alkenyl compounds) focus methodologies (boronation alkyl (pseudo)halides, derivatives carboxylic alcohols, primary amines, boronative C−H activation, novel approaches alkene hydroboration, 1,2‐metallate‐type rearrangements).

Language: Английский

Citations

64
Enantioselective Allylation of Alkenyl Boronates Promotes a 1,2-Metalate Rearrangement with 1,3-Diastereocontrol DOI
Colton R. Davis,

Irungu K. Luvaga,

Joseph M. Ready

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(13), P. 4921 - 4927

Published: March 23, 2021

Alkenyl boronates add to Ir(π-allyl) intermediates with high enantioselectivity. A 1,2-metalate shift forms a second C–C bond and sets 1,3-stereochemical relationship. The three-component coupling provides tertiary boronic esters that can undergo multiple additional functionalizations. An extension trisubstituted olefins three contiguous stereocenters.

Language: Английский

Citations

63
The Impact of Boron Hybridisation on Photocatalytic Processes DOI Creative Commons

Alessandro Marotta,

Callum E. Adams,

John J. Molloy

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: June 24, 2022

Recently the fruitful merger of organoboron chemistry and photocatalysis has come to forefront organic synthesis, resulting in development new technologies access complex (non)borylated frameworks. Central success this combination is control boron hybridisation. Contingent on photoactivation mode, as its neutral planar form or tetrahedral boronate can be used regulate reactivity. This Minireview highlights current state art photocatalytic processes utilising compounds, paying particular attention role hybridisation for target transformation.

Language: Английский

Citations

55
Ir‐Catalyzed Enantioselective Synthesis of gem‐Diborylalkenes Enabled by 1,2‐Boron Shift DOI

Jianfei Ge,

Xi‐Zhang Zou,

Xinru Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: June 15, 2023

Abstract Asymmetric cross‐couplings based on 1,2‐carbon migration from B‐ate complexes have been developed efficiently to access valuable organoboronates. However, enantioselective reactions triggered by 1,2‐boron shift remained be unaddressed synthetic challenge. Here, Ir‐catalyzed asymmetric allylic alkylation enabled was developed. In this reaction, we disclosed that excellent enantioselectivities were achieved through an interesting dynamic kinetic resolution (DKR) process of carbonates at the elevated temperature. Notably, highly (bis‐boryl)alkenes array diversifications versatile molecules. Extensive experimental and computational studies conducted elucidate reaction mechanism DKR clarify origin enantioselectivities.

Language: Английский

Citations

27
Photogeneration of α-Bimetalloid Radicals via Selective Activation of Multifunctional C1 Units DOI Creative Commons

Lewis McGhie,

Alessandro Marotta,

Patrick O. Loftus

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 15850 - 15859

Published: May 28, 2024

Light-driven strategies that enable the chemoselective activation of a specific bond in multifunctional systems are comparatively underexplored comparison to transition-metal-based technologies, yet desirable when considering controlled exploration chemical space. With current drive discover next-generation therapeutics, reaction design enables strategic incorporation an sp3 carbon center, containing multiple synthetic handles for subsequent space would be highly enabling. Here, we describe photoactivation ambiphilic C1 units generate α-bimetalloid radicals using only Lewis base and light source directly activate C–I bond. Interception these transient with various SOMOphiles rapid synthesis organic scaffolds (B, Si, Ge) orthogonal activation. In-depth theoretical mechanistic studies reveal prominent role 2,6-lutidine forming photoactive charge transfer complex stabilizing situ generated iodine radicals, as well influential boron p-orbital activation/weakening This simple efficient methodology enabled expedient access functionalized 3D frameworks can further derivatized available technologies C–B C–Si

Language: Английский

Citations

13
1,n-Bisborylalkanes via Radical Boron Migration DOI Creative Commons
Dinghai Wang, Christian Mück‐Lichtenfeld, Armido Studer

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(20), P. 9119 - 9123

Published: May 4, 2020

A systematic study of radical boron migration in diboronate complexes to form synthetically valuable 1,

Language: Английский

Citations

64
Allylboronic Esters as Acceptors in Radical Addition, Boron 1,2-Migration, and Trapping Cascades DOI Creative Commons

Kalipada Jana,

Armido Studer

Organic Letters, Journal Year: 2022, Volume and Issue: 24(4), P. 1100 - 1104

Published: Jan. 26, 2022

Radical 1,3-carboheteroarylation and 1,3-hydroalkylation of allylboronic esters comprising a 1,2-boron shift is reported. Allylboronic are generally used in synthesis as allylation reagents, where the boronic ester moiety gets lost. In introduced cascades, alkylboronic obtained with boron entity remaining product. The carboheteroarylation conducted without metal catalyst, achieved using iron catalysis. Both reactions work efficiently under mild conditions.

Language: Английский

Citations

30
Asymmetric Synthesis of Chiral 1,2‐Bis(Boronic) Esters Featuring Acyclic, Non‐Adjacent 1,3‐Stereocenters DOI

Xia‐Min Jiang,

Chong‐Lei Ji,

Jianfei Ge

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(5)

Published: Dec. 15, 2023

The construction of acyclic, non-adjacent 1,3-stereogenic centers, prevalent motifs in drugs and bioactive molecules, has been a long-standing synthetic challenge due to acyclic nucleophiles being distant from the chiral environment. In this study, we successfully synthesized highly valuable 1,2-bis(boronic) esters featuring nonadjacent 1,3-stereocenters. Notably, reaction selectively produces migratory coupling products rather than alternative deborylative allylation or direct byproducts. This approach introduces new activation mode for selective transformations gem-diborylmethane asymmetric catalysis. Additionally, found that other gem-diborylalkanes, previously challenging steric hindrance, also participated reaction. incorporation 1,2-bis(boryl)alkenes facilitated diversification alkenyl two boron moieties our target compounds, thereby enabling access broad array versatile molecules. DFT calculations were performed elucidate mechanism shed light on factors responsible observed excellent enantioselectivity diastereoselectivity. These determined arise ligand-substrate repulsions syn-addition transition state.

Language: Английский

Citations

22