ABSTRACT
Formation of new chemical species has been achieved under an electric field by the use of the scanning tunneling microscope break junction technique, yet simultaneous implementation of catalytic reactions both at the organic/metal interface and in the bulk solution remains a challenging task. Herein, we show that n-butyl-substituted organotin-terminated benzene undergoes both an efficient cleavage of the terminal tributyltin group to form a covalent Au-C bond and a homocoupling reaction to yield biphenyl product when subjected to an electric field in the vicinity to Au electrodes. By using ex situ characterization of high-performance liquid chromatography with an UV-vis detector, we demonstrate that the homocoupling reaction can occur with high efficiency under an extremely low tip bias voltage of â¼5 mV. Additionally, we show that the efficiency of the homocoupling reaction varies significantly in different solvents; the choice of the solvent proves to be one of the methods for modulating this reaction. By synthesizing and testing varied molecular backbone structures, we show that an extended biphenyl backbone undergoes homocoupling to form a quarterphenylene backbone, and the C-C coupling reactions are prohibited when additional aurophilic or bulky chemical groups that exhibit a steric blockage are introduced.
ABSTRACT
Our study unveils a novel approach to accessing boryl radicals through the spontaneous homolytic cleavage of B-B bonds. We synthesized a hexaaryl-substituted diboron(6) dianion, 1, via the reductive B-B coupling of 9-borafluorene. Intriguingly, compound 1 exhibits the ability to undergo homolytic B-B bond cleavage, leading to the formation of boryl radical anions, as confirmed by EPR studies, in the presence of the 2.2.2-cryptand at room temperature. Moreover, it directly reacts with diphenylacetylene, producing an unprecedented 1,6-diborylated allene species, where the phenyl ring is dearomatized. Density functional theory computational studies suggest that homolytic B-B bond cleavage is favored in the reaction path, and the formation of the boryl radical anion is crucial for dearomatization. Additionally, it achieves the dearomative diborylation of anthracene and the activation of elemental sulfur/selenium under mild conditions. The borylation products have been successfully characterized by NMR spectra, HRMS, and X-ray single-crystal diffraction.
ABSTRACT
A catalyst-free 1,2-diborylation of aryllithium with tetra(o-tolyl)diborane(4) has been achieved, giving a series of 1,2-diborylaryl lithium species in excellent yields under mild reaction conditions, which leads to 1,2-di(tolyl)borylarenes in 60-91 % yields upon treatment with the hydride-abstracting reagent. In these transformations, one sp2 C-H of arene is activated and both boryl units are utilized to build two new (sp2 )C-B bonds. This represents a new strategy for selective arene diborylation. Density functional theory (DFT) calculations suggest that an aromatic nucleophilic substitution is a key step in the formation of the products.
ABSTRACT
Electron-precise B-B bonded compounds are valuable reagents in organic syntheses, which can be used as key starting material for the synthesis of functionalized organoboranes. Bis(pinacolato)diborane(4) B2 pin2 and its derivatives are among the most studied diboron species. However, their B-B bonds usually need to be activated by transition metal catalysts or bases for further transformations. Recently, many well-designed/reactive electron-precise B-B bonded compounds have been developed, which could facilitate direct reactions with small molecules, unsaturated substrates, and electrophiles. This review highlights the synthesis, structure, and reactivity of neutral and anionic B-B bonded compounds.
ABSTRACT
A transition-metal-free coupling protocol between iodocarboranes and terminal alkynes enabled by light at room temperature has been developed, leading to the synthesis of a variety of 1-alkynyl-o-carboranes. Moreover, following this strategy, the introduction of 1-I-3-aryl-o-carboranes or 1-I-2-aryl-o-carboranes results in the formation of o-carborane-fused cyclics. Interestingly, when 1-I-3-(p-R-C6H4)-o-carboranes are chosen as coupling partners, unexpected R-group migration products are also isolated. On the basis of the results of control experiments and isolation of the key intermediates, a possible reaction mechanism is then proposed, involving the formation of spiro radical species.
ABSTRACT
A redox-switchable self-assembled ZnII 4 L6 cage was synthesized that contains naphthalenediimide (NDI) motifs. Its reduction lent these NDI panels persistent radical anion character. The redox activity of this cage allows it to act as a catalyst for the oxidative coupling of different tetraaryl borates to give biaryls. The catalytic activity of the cage was enhanced following its binding of C60 , which implies a mechanism that does not involve encapsulation of the substrate.
ABSTRACT
We present a new concept to control the conformations of molecules in the excited state through harvesting negative hyperconjugation. The strategy was realized with the 2,3,1,4-benzodiazadiborinane scaffold, which was prepared by a new synthetic procedure. Photochemical studies identified dual light emission, which was assigned to well-defined conformers. The emission at longer wavelength can be switched off by restricting the rotational degrees of freedom in the solid state as well as by controlling the energy levels of the excited states through adjusting the solvent polarity.
ABSTRACT
We report an air-stable bisboron complex as an efficient catalyst for the inverse electron-demand Diels-Alder (IEDDA) reaction of 1,2-diazine as well as 1,2,4,5-tetrazine. Its stability towards air and moisture was demonstrated by NMR studies enabling its application in organic transformations without glovebox. A one-pot procedure for its synthesis was developed starting from 1,2-bis(trimethylsilyl)benzene greatly enhancing its practicality. Comparative reactions were carried out to evaluate its catalytic activity in IEDDA reactions of diazine including phthalazine as well as 1,2,4,5-tetrazine.
ABSTRACT
We report the formation of a stable neutral diboron diradical simply by coordination of an aromatic dinitrogen compound to an ortho-phenyldiborane. This process is reversible upon addition of pyridine. The diradical species is stable above 200 °C. Computations are consistent with an open-shell triplet diradical with a very small open-shell singlet-triplet energy gap that is indicative of the electronic disjointness of the two radical sites. This opens a new way of generating stable radicals with fascinating electronic properties useful for a large variety of applications.
ABSTRACT
A new transition-metal-free mode for the catalytic reduction of carbon dioxide via bidentate interaction has been developed. In the presence of Li2[1,2-C6H4(BH3)2], CO2 can be selectively transformed to either methane or methanol, depending on the reducing agent. The bidentate nature of binding is supported by X-ray analysis of an intermediate analogue, which experiences special stabilization due to aromatic character in the bidentate interaction. Kinetic studies revealed a first-order reaction rate. The transformation can be conducted without any solvent.
ABSTRACT
The storage of energy in a safe and environmentally benign way is one of the main challenges of today's society. Ammonia-borane (AB=NH3 BH3 ) has been proposed as a possible candidate for the chemical storage of hydrogen. However, the efficient release of hydrogen is still an active field of research. Herein, we present a metal-free bis(borane) Lewis acid catalyst that promotes the evolution of up to 2.5â equivalents of H2 per AB molecule. The catalyst can be reused multiple times without loss of activity. The moderate temperature of 60 °C allows for controlling the supply of H2 on demand simply by heating and cooling. Mechanistic studies give preliminary insights into the kinetics and mechanism of the catalytic reaction.
ABSTRACT
Multifluorinated aromatics serve as supramolecular synthons in the research of organic electro-optic (EO) materials by exploiting π-π stacking interaction between the aromatic hydrocarbon and multifluorinated aromatic groups for performance improvement. However, non-classical hydrogen bonding remains largely unexplored in fluorinated EO dendrimers. In this study, three Fréchet-type generation 1 benzyl ether co-dendrons were synthesized by replacing one benzyl group with 2,3,5,6-tetrafluorobenzyl (p-HF4Bz), pentafluorobenzyl (C6F5Bz), and 2,3,4,5-tetrafluorobenzyl (o-HF4Bz) groups, to afford the benzoic acid derivatives D1, D2, and D3, which were further bonded to the donor and π-bridge moieties to afford three co-dendronized push-pull phenyltetraene chromophores EOD1, EOD2, and EOD3, respectively. The weak C-Hâ â â X (X=O, F) interactions in the crystal structure of D1 cumulatively add to the benzoic acid dimers to form an extended hydrogen-bonded network, while D2 is crystallized into a centric one-dimensional chain with strong intermolecular interactions. The poled films of EOD1 with PMMA exhibited the largest and most stable EO activity with optical homogeneity among the series. The results identify the effectiveness of weak but favorable hydrogen bonds enabled by the enhanced carbon acidity of p-HF4Bz synthon in D1, over the interactions in D2 and D3, for the rational design of supramolecular EO dendrimers.
ABSTRACT
Group 1 elements exhibit the lowest electronegativity values in the Periodic Table. The chemical reduction of Group 1 metal cations M+ to M(0) is extremely challenging. Common tetraaryl borates demonstrate limited redox properties and are prone to decomposition upon oxidation. In this study, by employing simple yet versatile bipyridines as ligands, we synthesized a series of redox-active borate anions characterized by NMR and X-ray single-crystal diffraction. Notably, the borate anion can realize the reduction of Li+, generating elemental lithium metal and boron radical, thereby demonstrating its potent reducing ability. Furthermore, it can serve as a powerful two-electron-reducing reagent and be readily applied in various reductive homo-coupling reactions and Birch reduction of acridine. Additionally, this borate anion demonstrates its catalytic ability in the selective two-electron reduction of CO2 into CO.
ABSTRACT
Chemoselective modification of specific residues within a given protein poses a significant challenge, as the microenvironment of amino acid residues in proteins is variable. Developing a universal molecular platform with tunable chemical warheads can provide powerful tools for precisely labeling specific amino acids in proteins. Cysteine and lysine are hot targets for chemoselective modification, but current cysteine/lysine-selective warheads face challenges due to cross-reactivity and unstable reaction products. In this study, a versatile fluorescent platform is developed for highly selective modification of cysteine/lysine under biocompatible conditions. Chloro- or phenoxy-substituted NBSe derivatives effectively labeled cysteine residues in the cellular proteome with high specificity. This finding also led to the development of phenoxy-NBSe phototheragnostic for the diagnosis and activatable photodynamic therapy of GSH-overexpressed cancer cells. Conversely, alkoxy-NBSe derivatives are engineered to selectively react with lysine residues in the cellular environment, exhibiting excellent anti-interfering ability against thiols. Leveraging a proximity-driven approach, alkoxy-NBSe probes are successfully designed to demonstrate their utility in bioimaging of lysine deacetylase activity. This study also achieves integrating a small photosensitizer into lysine residues of proteins in a regioselective manner, achieving photoablation of cancer cells activated by overexpressed proteins.
Subject(s)
Cysteine , Fluorescent Dyes , Lysine , Lysine/chemistry , Cysteine/chemistry , Cysteine/metabolism , Humans , Fluorescent Dyes/chemistry , Photochemotherapy/methods , Cell Line, TumorABSTRACT
The chemistry of "frustrated Lewis pairs" (FLPs) has become a rapidly evolving field since it was introduced 6 years ago. It offers new strategies for small molecule activation and organic synthesis which have long been dominated by transition metals. This chapter focuses on the recent development of organoborane compounds and their applications in FLP chemistry. Modifying the organoboranes along with optimizing the Lewis base partners results in a wide range of reactivities, such as small molecule activation and hydrogenation catalysis.
ABSTRACT
Out with the metal: Metal-free hydrogenation of unfunctionalized olefins can be achieved by employing HB(C6F5)2 as the catalyst. The key step in the catalytic reaction is believed to involve a novel borane-mediated σ-bond metathesis, which has been investigated both experimentally and theoretically.
ABSTRACT
A tetra(o-tolyl) (µ-hydrido)diborane(4) anion 1, an analogue of [B2H5]- species, was facilely prepared through the reaction of tetra(o-tolyl)diborane(4) with sodium hydride. Unlike common sp2-sp3 diborane species, 1 exhibited a σ-B-B bond nucleophilicity towards NHC-coordinated transition-metal (Cu, Ag, and Au) halides, resulting in the formation of η2-B-B bonded complexes 2 as confirmed by single-crystal X-ray analyses. Compared with 1, the structural data of 2 imply significant elongations of B-B bonds, following the order Au > Cu > Ag. DFT studies show that the diboron ligand interacts with the coinage metal through a three-center-two-electron B-M-B bonding mode. The fact that the B-B bond of the gold complex is much prolonged than the related Cu and Ag compounds might be ascribed to the superior electrophilicity of the gold atom.
ABSTRACT
The synthesis of alkenylated-o-carboranes via photoalkenylation of iodocarboranes with unactivated alkenes has been achieved. This strategy features a transition metal-free protocol, a light-promoted reaction under mild reaction conditions, broad substrate scope and good functional group tolerance. Control experiments suggest that the reaction may involve the cage C-centered radical species.
ABSTRACT
Small ring compounds are fascinating molecules and have been used as valuable compounds in organic synthesis. In this study, a carborane-fused four-membered boracycle bearing an electron precise B-B bond, 1,2-[BBrSMe2]2-o-C2B10H10, was synthesized via the reaction of 1,2-Li2-o-carborane with B2Br4(SMe2)2. This novel boracycle can be used as a "strain-release" compound to achieve diboration of alkenes and alkynes, leading to the generation of ring-expansion products. Interestingly, when bis(trimethylsilyl) acetylene was employed, an allene-functionalized six-membered boracycle was obtained. Moreover, DFT calculations were conducted to shed light on the reaction mechanism.
ABSTRACT
New types of ligands, carborane-fused cyclopentenyl and dicarbollyl-fused cyclopentene, were conveniently prepared in high yields. Treatment of the lithium salt of carborane-fused cyclopentenyl anion, [1,2-[C(Me)CHC(Ph)]-1,2-C2B10H10]Li, with [Cp*RuCl]4 generated an 18-electron complex [η3:η2-(PhCCHCMe)C2B10H10]Ru(η5-Cp*). On the other hand, reaction of the dicarbollide salt, [7,8-(CH2CH[double bond, length as m-dash]CMe)-7,8-C2B9H9]Na2 with [(η6-p-cymene)RuCl2]2 or CoCl2/CpNa, afforded the salt metathesis product [η5-(CH2CH[double bond, length as m-dash]CMe)C2B9H9]Ru(η6-p-cymene) or [η5-(CH2CH[double bond, length as m-dash]CMe)C2B9H9]Co(η5-C5H5) in good yields. In contrast, [7,8-(CH2CH[double bond, length as m-dash]CMe)-7,8-C2B9H9]Na2 reacted with Ni(dppp)Cl2 (dppp = 1,3-bis(diphenylphosphino)propane) to give another 18-electron metallacarborane [η5-(CH2CH[double bond, length as m-dash]CMe)C2B9H9]Ni(dppp), in which one of the cage carbon atoms has been isomerized to the lower belt of the cage due to steric reasons. All these new metallacarborane compounds were fully characterized by NMR spectroscopy, high-resolution mass spectroscopy and single-crystal X-ray analyses.