Copper-mediated synthesis of N,N''''-diarylhydrazines from boronic acids

N,N0-Diarylhydrazines have been prepared via the reaction of N-Boc-aryl hydrazines with boronic acids mediated by copper acetate. This mild reaction condition tolerates the presence of a variety of functional groups.     

Palladium-catalyzed, copper(I)-mediated coupling of boronic acids and benzylthiocyanate. A cyanide-free cyanation of boronic acids

A new method for the synthesis of nitriles is described. As a complement to the classic cyanation of aryl halides using cyanide sources and a transition metal catalyst, the palladium-catalyzed cross-coupling of thiocyanates with boronic acids in the presence of copper(I) thiophene-2-carboxylate (CuTC) affords nitriles in good to excellent yields.     

(1-Methoxyvinyl)boronic and (1-chlorovinyl)boronic esters

(s)-Pinanediol (1-methoxyvinyl)boronate ( 1 ) was prepared from (1-methoxyvinyl)-lithium and triisopropyl borate followed by (s)-pinanediol. Attempted reaction with (dichloromethyl)lithium failed, and reaction with butylmagnesium chloride followed by acetic acid yielded a mixture of diastereomers of (s)-pinanediol (1-methoxy-1-methyl-pentyl)boronate ( 2 ). (s)-Pinanediol (1-chlorovinyl)boronate ( 4 ) has been prepared by dehydrochlorination of (s)-pinanediol 1,1-dichloroethylboronate ( 3 ) with lithium chloride in dimethylformamide. Reaction of 4 with (dichloromethyl)lithium yielded (s)-pinanediol (1S)-(1,2-dichloroallyl)boronate ( 5 ) in 92% diastereomeric excess. Reaction of 5 with RMgX resulted in a 3 : 1 ratio of displacement of the 1-Cl from carbon by R to displacement of the entire 1,2-dichloroallyl group from boron by R. With lithium benzyl oxide, displacement of the 1-Cl from 5 failed entirely. Reaction of 4 with (dibromomethyl)lithium was inefficient and yielded a gross mixture of diastereomers.     

Synthesis of a (β-acetamido-α-acetoxyethyl)boronic ester via azido boronic esters

(Azidomethyl)boronic esters of 1,2-dicyclohexyl-1,2-ethanediol (“DICHED”) and pinanediol have been prepared from the corresponding (bromomethyl)boronic esters. Conversion to (2-azido-1-chloro- or bromoethyl)boronic esters by reaction with a (dihalomethyl)lithium followed. Attempted displacement of halide from DICHED (2-azido-1-haloethyl)boronates with alkoxides failed. Reaction of either pinanediol or DICHED (2-azido-1-chloromethyl)boronate with sodium acetate in acetic acid yielded the 1-acetoxy derivative as a ∼1:1 mixture of diastereomers, indicating probable involvement of an α-boryl carbocation intermediate. Hydrogenation of the pinanediol azido boronic ester over platinum in a solution of hydrogen chloride in dioxane was accompanied by deacetylation to form the impure (2-amino-1-hydroxyethyl)boronic ester hydrochloride. Attempted purification of this material resulted in deboronation to ethanolamine. Acetylation yielded pinanediol (2-acetamido-1-acetoxyethyl)boronate.     

A novel redox-sensitive protecting group for boronic acids, MPMP-diol

A new boronic acid protecting group, 1-(4-methoxyphenyl)-2-methylpropane-1,2-diol (MPMP-diol), has been developed. Both protection and deprotection can be accomplished under mild conditions with quantitative conversions. The deprotection can be carried out using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ).     

Homologation of boronic esters with trimethylsilylchloromethyllithium

Trimethylsilylchloromethyllithium adds to boronic esters to form ate complexes which rearrange with displacement of chloride to form the homologous α-trimethylsilyl boronic esters in high yields.     

Copper-mediated oxidative trifluoromethylation of boronic acids

A copper-mediated oxidative cross-coupling of aryl- and alkenylboronic acids with (trifluoromethyl)trimethylsilane (Me(3)SiCF(3)) under mild conditions has been developed. This method allows a wide range of functional group tolerant trifluoromethylated arenes and alkenes to be easily prepared. This oxidative trifluoromethylation has the potential to introduce trifluoromethyl groups into advanced, highly functionalized organic molecules.     

Facile preparation of fullerenyl boronic esters

The fullerendiol C₆₀(OH)₂(OOt-Bu)₄ 1 reacts with various arylboronic acids ArB(OH)₂ to form fullerene-containing boronic esters C₆₀(O₂BAr)(OOt-Bu)₄ in up to 95% yield depending on the structure of aryl group. Bis(pinacolato)diboron (B(OCMe₂)₂)₂ also reacts with 1 to form C₆₀(O₂BB(OCMe₂)₂)(OOt-Bu)₄. The bisboronic ester C₆₀(O)(O₂BAr)₂(OOt-Bu)₂ was also obtained starting from a tetrahydroxyl fullerene derivative C₆₀(O)(OH)₄(OOt-Bu)₂. The fullerenyl boronic esters are moderately stable in air. Single crystal X-ray structure of C₆₀(O₂BPh)(OOt-Bu)₄ was obtained.     

Electrosynthesis of boronic acids and esters

Electrosynthesis offers an interesting alternative to the classical synthesis of organoboronic derivatives. Aryl-, allyl- and benzylboronic acids can be prepared via the reduction of organic halides in the presence of trialkylborates or pinacolborane. Electrochemical methodology avoids the use of noble metals and of low temperatures. It also allows the use of more accessible organic chlorides as starting substrates. With dihalogenated derivatives, good borylation selectivities can be obtained.

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Glucose recognition by a supramolecular complex of boronic acid fluorophore with boronic acid-modified cyclodextrin in water

A boronic acid fluorophore (C1-APB)/boronic acid-modified γ-cyclodextrin (3-PB-γ-CyD) complex as a supramolecular sensor has been designed for selective glucose recognition in water. The fluorescent response behavior of the C1-APB/3-PB-γ-CyD complex under various pH conditions revealed that a C1-APB/3-PB-γ-CyD complex solution containing glucose showed a large increase in the fluorescence intensity under alkaline pH conditions. In contrast, only small increases in the fluorescence intensity were noted for fructose and without sugar solutions. The observed response selectivity for the C1-APB/3-PB-γ-CyD complex was on the order of glucose > galactose, mannose > fructose. The evidence on a large value of the inclusion constant (K(L·CyD) = 6.5 × 10(3) M(-1)), a marked broadening of the (1)H NMR spectra, and an enhancement of induced circular dichloism (ICD) intensity for the C1-APB/3-PB-γ-CyD complex by glucose binding supported the multi-point interaction of the C1-APB/3-PB-γ-CyD complex with glucose. These results demonstrated that the C1-APB/3-PB-γ-CyD complex functioned as an efficient supramolecular sensor for selective glucose recognition in water.     

Synthesis, evaluation, and computational studies of naphthalimide-based long-wavelength fluorescent boronic Acid reporters

Boronic acids that change fluorescence properties upon sugar binding are very useful for the synthesis of carbohydrate sensors. Along this line, boronic acids that fluoresce beyond 500 nm are especially useful. A series of boronic acid fluorescent reporter compounds based on the 4-amino-1,8-naphthalimide structure have been synthesized (1a-d) and evaluated under near physiological conditions. These compounds showed good water solubility and significant changes in fluorescence properties after binding with sugars, with the emission wavelength being at around 570 nm. Analogues in this series with different substitutions showed similar properties. We have also examined the mechanism of the observed fluorescence changes for these compounds.     

超声条件下制备单取代硼酸

本文报道以硼酸三丁酯为原料与卤代烃，金属镁粉在室温下经超声辐射制备单取代硼酸的结果。该方法操作简单，反应速度快，并得到满意的产率，有一定的应用价值。     

雪松烷二醇硼酸酯的合成及其不对称同系化反应

报道了手性试剂雪松烷二醇硼酸酯(3)的合成及其和二氯甲基锂进行不对称同系化反应,生成α-氯代硼酸酯4R和4S,其R/S的比率在25:1以上,并且有手性助剂容易回收的特点。通过对同系化产物4cR的单晶X衍射分析,发现其分子中的1,3-二氧杂-2-硼杂环戊烷为非平面结构,文中就这一结构特点进行了初步讨论,解释了雪松烷二醇硼酸酯容易水解的原因。     

The effect of boronic acid acidity on performance of viologen-based boronic acids in a two-component optical glucose-sensing system

A two-component saccharide sensing system using the fluorescent dye, hydroxypyrene trisulfonic acid, combined with a boronic acid functional viologen as a receptor/quencher in pH 7.4 buffer solution has been further investigated. The effect of substituents on the acidity of the boronic acid was measured. The boronic acid pK_a changed in the expected manner when electron donating or withdrawing groups were present. The glucose binding constants were dependent on pK_a, but no simple correlation was observed for the Stern-Volmer quenching constants and the fluorescence signal modulation.     

Suzuki-Miyaura cross-couplings of secondary allylic boronic esters

Palladium-catalyzed cross-coupling reactions of secondary allylic boronic esters with iodoarenes were demonstrated under the conditions previously described for the coupling of benzylic substrates. The regioselectivity of the process was largely dictated by the pattern of olefin substitution.     

Ultrasensitive fluorescent responses of water-soluble, zwitterionic, boronic acid-bearing, regioregular head-to-tail polythiophene to biological species

Water-soluble regioregular head-to-tail zwitterionic fluorescent conjugated boronic acid-bearing polythiophene (polymer 2) was prepared through a postpolymerization quaternization of a pyridine group of 3-pyridineboronic acid with bromide groups of regioregular head-to-tail poly(3-bromohexylthiophene) (polymer 1). Titration of monosaccharides, lactose, ascorbic acid, or dopamine with 0.1 M phosphate buffer (pH 7.4), containing 4.0 microM of polymer 2, results in significant concentration-dependent quenching of the polymer fluorescence. The polymer displays an optimum response to the biological species at pH 7.0. The binding constants of polymer 2 with mannose, fructose, glucose, galactose, vitamin C, dopamine, and lactose are 3.33 x 10(4), 1.13 x 10(5), 1.23 x 10(5), 1.69 x 10(5), 3.17 x 10(5), 3.27 x 10(5), and 4.60 x 10(5), respectively.     

Synthesis,characterization, and star polymer assembly of boronic acid end‐functionalized polycaprolactone

Boronic acid end‐functionalized polycaprolactone (PCL) polymers were synthesized by ring‐opening polymerization using a pinacol boronate ester‐containing (Bpin) initiator. The polymerization provides access to boron‐terminated polymers (i.e. Bpin‐PCL‐OH) with narrow molecular weight distributions (PDI = 1.09). Postsynthetic manipulation of the polymer's terminal hydroxyl group by copper‐catalyzed azide‐alkyne cycloaddition chemistry provides a series of bis end‐functionalized polymers with significant structural diversity at the termini. Deprotection of the boronate ester end group was accomplished with an acidic solid phase DOWEX resin. The boronate ester deprotection methodology does not result in hydrolysis of the polymeric backbone. The boronic acid‐tipped polymers were converted into star polymer assemblies using thermal dehydration and ligand‐facilitated trimerization. Thermal dehydration of (HO)₂B‐PCL‐OAc to the corresponding boroxine‐based star polymer assembly was inefficient and lead to degradation products. Ligand‐facilitated trimerization using either pyridine or 7‐azaindole as the Lewis base was efficient and mild. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Copper-mediated O-arylation of lactols with aryl boronic acids

A novel and efficient method to access phenolic glycosides has been established by using copper-mediated coupling reaction of aryl boronic acids with hemiacetals. The reaction enjoyed a wide range of substrate scope, and many phenolic glycosides can be synthesized in good yields.     

The thermal decomposition of salts of boronic acids

Salts with the formula M[RB(OH)₃] (where M is Li, Na or K, and R is C₆H₅ or C₆H₁₁) and M[C₆H₅B(OH)₃]₂ (where M is Ca, Sr or Ba) were prepared. The thermal decomposition in air and in nitrogen proceeded through a series of intermediate compounds to the respective anhydrous metaborate salt. The possible nature of these intermediate compounds is considered.