Facile Access to Cyclopropylboronates via Stereospecific Deborylative Cyclization: A Leaving Group‐Assisted Activation of Geminal Diborons DOI
Xinyi Chen,

Feng‐Chen Gao,

Peng‐Fei Ning

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 24, 2023

Herein we reported a transition metal-free deborylative cyclization strategy, based on which two routes have been developed, generating racemic and enantioenriched cyclopropylboronates. The of geminal-bis(boronates) bearing leaving group was highly diastereoselective, tolerating few functional groups applicable to heterocycles. When optically active epoxides were used as the starting materials, cyclopropylboronates could be efficiently prepared with >99 % stereospecificity. Mechanistic studies showed that at γ-position played crucial role significantly promoted activation gem-diboron moiety.

Language: Английский

Iridium‐Catalysed C−H Borylation of Heteroarenes: Balancing Steric and Electronic Regiocontrol DOI Creative Commons
Jay S. Wright, Peter J. H. Scott, Patrick G. Steel

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(6), P. 2796 - 2821

Published: March 23, 2020

The iridium-catalysed borylation of aromatic C−H bonds has become the preferred method for synthesis organoboron compounds. reaction is highly efficient, tolerant a broad range substituents and can be applied to both carbocyclic heterocyclic substrates. regioselectivity activation dominated by steric considerations there have been considerable efforts develop more selective processes less constrained However, most these focused on benzenoid-type substrates in contrast, heteroarenes remain much desired but challenging with position and/or nature heteroatom(s) significantly affecting reactivity regioselectivity. This review will survey heteroarenes, focusing influence electronic effects regiochemical outcome and, linking current mechanistic understandings, provide insights what currently possible where further developments are required.

Language: Английский

Citations

143
Boron insertion into alkyl ether bonds via zinc/nickel tandem catalysis DOI
Hairong Lyu, Ilia Kevlishvili, Xuan Yu

et al.

Science, Journal Year: 2021, Volume and Issue: 372(6538), P. 175 - 182

Published: April 9, 2021

Slipping boron into alkyl ethers The carbon–oxygen bonds that hold together are relatively inert. Lyu et al. report zinc and nickel can team up to insert between the carbon oxygen using an unusual mechanism. First, a dibromoborane pries open bond with help from ion. Next, stitches boron, oxidation of metallic starts cycle over again. Versatile reactivity at inserted center then add carbons original ether or swap out for nitrogen. Science , this issue p. 175

Language: Английский

Citations

119
Iridium-Catalyzed Asymmetric Difunctionalization of C–C σ-Bonds Enabled by Ring-Strained Boronate Complexes DOI Creative Commons

Hong‐Cheng Shen,

Mihai V. Popescu, Ze‐Shu Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(30), P. 16508 - 16516

Published: July 20, 2023

Enantioenriched organoboron intermediates are important building blocks in organic synthesis and drug discovery. Recently, transition metal-catalyzed enantioselective 1,2-metalate rearrangements of alkenylboronates have emerged as an attractive protocol to access these valuable reagents by installing two different carbon fragments across C═C π-bonds. Herein, we report the development iridium-catalyzed asymmetric allylation-induced rearrangement bicyclo[1.1.0]butyl (BCB) boronate complexes enabled strain release, which allows difunctionalization C-C σ-bonds, including dicarbonation carboboration. This provides a variety enantioenriched three-dimensional 1,1,3-trisubstituted cyclobutane products bearing boronic ester that can be readily derivatized. Notably, reaction gives trans diastereoisomers result from anti-addition σ-bond, is contrast syn-additions observed for reactions promoted PdII-aryl other electrophiles our previous works. The diastereoselectivity has been rationalized based on combination experimental data density functional theory calculations, suggest BCB highly nucleophilic react via early states with low activation barriers.

Language: Английский

Citations

47
Divergent Synthesis of Fluoroalkyl Ketones through Controlling the Reactivity of Organoboronate Complexes DOI
Gang Zhou,

Zhuanzhuan Guo,

Shanshan Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 4026 - 4035

Published: Feb. 1, 2024

Herein, we report a divergent synthesis of fluoroalkyl ketones through visible-light-induced reactions between readily available organoboronic esters and acylsilanes. Selective control the reactivity in situ generated organoboronate complexes is key to achieving transformations. Under basic conditions, undergo deboronative fluoride elimination, resulting formation enol silyl ethers as intermediates that react with various electrophiles generate defluorinated products. Moreover, combination peroxide, 1,2-shift group favored over elimination ketal intermediates, leading This transition-metal-free reaction operationally simple, aryl, alkenyl, alkyl boronic are all suitable substrates. The synthetic potential has been demonstrated by gram-scale facile bioactive molecules including zifrosilone its analogs.

Language: Английский

Citations

31
Ni-catalysed assembly of axially chiral alkenes from alkynyl tetracoordinate borons via 1,3-metallate shift DOI

Xingxing Ma,

Mengwei Tan,

Luo Li

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(1), P. 42 - 53

Published: Jan. 1, 2024

Language: Английский

Citations

30
Enantioselective Copper-Catalyzed Ring-Opening Diboration of Arylidenecyclopropanes to Access Chiral Skipped 1,4- and 1,3-Diboronates DOI
Wenrui Zheng,

Boon Beng Tan,

Shaozhong Ge

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5366 - 5374

Published: Feb. 14, 2024

Two enantioselective approaches to synthesize chiral skipped diboronate compounds have been developed, relying on copper-catalyzed one-pot asymmetric ring-opening diboration of arylidenecyclopropanes. A wide range arylidenecyclopropanes react smoothly with HBpin in the presence CuOAc and (R)-DTBM-Segphos, affording 1,4-diboronates high enantioselectivity (up 99% ee). Meanwhile, a variety selectively B2pin2 (S,S)-Ph-BPE sequential addition MeOH, providing 1,3-diboronates 98% These enantioenriched 1,3- can undergo various enantiospecific transformations minimal loss their enantiopurity. Mechanistic studies reveal that these two processes start CuH-catalyzed hydroboration form mixture Z/E-homoallyl boronate intermediates, which subsequently second or Cu-Bpin-catalyzed protoboration produce 1,3-diboronates, respectively.

Language: Английский

Citations

21
Planar Core and Macrocyclic Shell Stabilized Atomically Precise Copper Nanocluster Catalyst for Efficient Hydroboration of C–C Multiple Bond DOI Creative Commons
Badriah Alamer, Arunachalam Sagadevan, Mohammad Bodiuzzaman

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16295 - 16305

Published: May 30, 2024

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design development bond-forming reaction based on copper NCs are still in early stages. Herein, we report synthesis atomically nanocluster with a planar core unique shell, [Cu45(TBBT)29(TPP)4(C4H11N)2H14]2+ (Cu45) (TBBT: 4-tert-butylbenzenethiol; TPP: triphenylphosphine), yield via one-pot reduction method. The resulting structurally well-defined Cu45 is highly efficient catalyst for hydroboration alkynes alkenes. Mechanistic studies show that single-electron oxidation situ-formed ate complex enables formation boryl-centered radicals under mild conditions. This work demonstrates promise as C–B heteroatom reactions. compatible wide range alkenes functional groups producing hydroborated products.

Language: Английский

Citations

19
Facile Access to Quaternary Carbon Centers via Ni-Catalyzed Arylation of Alkenes with Organoborons DOI
Zi-Chao Wang, Lei Gao, Songyang Liu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

Quaternary carbon centers are widespread structural motifs, thus representing extensive interest in organic synthesis. We describe here an efficient nickel-catalyzed intermolecular, Markovnikov-selective arylation of minimally functionalized alkenes with stable organoborons, affording a broad range cyclic or acyclic quaternary under mild conditions. The utilization the diimine ligand is critical for high reactivity and chemoselectivity. Furthermore, using bulky chiral as Ni catalyst, stereocenters can be readily prepared levels enantiocontrol. Mechanism studies suggest that, before protonation, rare nickel shift from alkyl to aryl might occur.

Language: Английский

Citations

3
Site‐Selective 1,2‐Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis DOI
Shang‐Zheng Sun, Yaya Duan, Riccardo S. Mega

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(11), P. 4370 - 4374

Published: Jan. 7, 2020

A modular, site-selective 1,2-dicarbofunctionalization of vinyl boronates with organic halides through dual catalysis is described. This reaction proceeds under mild conditions and characterized by excellent chemo- regioselectivity. It thus represents a complementary new technique for preparing densely functionalized alkyl boron architectures from simple accessible precursors.

Language: Английский

Citations

140
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

128