低温Suzuki反应合成联苯及三联苯化合物

发展了一个低温下无配体钯催化溴代芳烃与芳基硼酸的Suzuki反应体系。该体系以醋酸钯为催化剂,无水碳酸钾为碱,乙醇水溶液为溶剂,无需加入任何配体,在0oC下即可高效催化溴代芳烃与芳基硼酸的Suzuki反应;反应的底物容忍性好,产品分离收率最高达97%。以溴代芳基N-甲基亚氨基二乙酸硼酸酯为砌块分子,通过调控反应温度,实现了砌块分子选择性Suzuki反应,从而一锅合成了不对称三联苯化合物,产品收率最高为81%。     

Kinetic scheme of homogeneous acid-catalyzed transformation of isopentenols

The reactions occurring in an equilibrium mixture of 3-methyl-1-buten-3-ol and 3-methyl-2-buten-1-ol in 24–49 % aqueous solutions of H₂SO₄ yield isoprene, 3-methyl-3-buten-1-ol, isobutylene, formaldehyde, 3-methylbutane-1,3-diol. Isobutylene is rapidly hydrated to give 2-methylpropan-2-ol. The presence of formaldehyde in the reaction mixture indicates that the transformations involve the reverse Prins reaction. On the basis of experimental and literature data, two most probable reaction schemes were suggested.Translated fromIzvestiya Akademii Nauk. Sertya Khimicheskaya, No. 5, pp. 867–870, May, 1995.     

资源化学研究进展*

本文总结了本课题组在资源化学领域的研究工作进展,内容涉及到天然资源化合物甾体皂甙元和非天然资源性化合物氟烷基磺酰氟的反应及其在有机合成中的应用。首先介绍了原子经济性地利用甾体皂甙元资源的策略与方法。为解决甾体皂甙元资源在工业利用过程产生的环境污染和资源浪费问题,我们发展了用30%双氧水代替铬酐氧化降解假甾体皂甙元的方法,使“百分之百”利用甾体皂甙元资源的理想成为现实。双氧水与乙酸原地产生的过氧酸直接氧化甾体皂甙元成为孕甾-16,20-二醇类化合物和4R-甲基-5羟基戊酸内酯,通过甾体皂甙元的非正常Baeyer-Villiger反应合成了甾体-16羟基-22-内酯类化合物和3R-甲基-5羟基戊酸内酯。所获甾体中间体和带甲基侧链的双官能团手性试剂被应用于部分甾体药物、昆虫信息素、香料和天然产物的合成中。另外还介绍了利用甾体皂甙元完整骨架合成目标分子的资源性化合物利用策略。本文第二部分内容介绍了氟烷基磺酰氟资源利用的策略和方式。反应共生是我们提高氟烷基磺酰氟资源利用率的新思路,基于共生反应概念,研究了邻二醇环氧化反应、烯烃环氧化反应和碳正离子重排等反应与氟烷基磺酰氟水解反应的共生反应,并且介绍了其合成应用实例。     

Reaction of 3,3-dichloropentane-2,4-dione with aromatic aldehydes under the conditions of Darzens reaction

3,3-Dichloropentane-2,4-dione reacts with aromatic aldehydes under the conditions of Darzens reaction to give 4-acetoxy-4-aryl-3,3-dichlorobutan-2-ones, the products of insertion into the -C-C bond. The reaction of ethyl dichloroacetylacetate with benzaldehyde yields a derivative of tricyclo[5.1.0.0^3,5]octane, rather than 2,6-bis(1-chlorobenzylidene)cyclohexane-1,4-dione, as the by-product.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1294–1298, July, 1995.     

One-Pot and Catalyst-Free Transformation of N-Protected 1-Amino-1-Ethoxyalkylphosphonates into Bisphosphonic Analogs of Protein and Non-Protein α-Amino Acids

Herein, we describe the development of one-pot transformation of α-ethoxy derivatives of phosphorus analogs of protein and non-protein α-amino acids into biologically important N-protected 1-aminobisphosphonates. The proposed strategy, based on the three-component reaction of 1-(N-acylamino)-1-ethoxyphosphonates with triphenylphosphonium tetrafluoroborate and triethyl phosphite, facilitates good to excellent yields under mild reaction conditions. The course of the reaction was monitored by ³¹P NMR spectroscopy, allowing the identification of probable intermediate species, thus making it possible to propose a reaction mechanism. In most cases, there is no need to use a catalyst to provide transformation efficiency, which increases its attractiveness both in economic and ecological terms. Furthermore, we demonstrate that the one-pot procedure can be successfully applied for the synthesis of structurally diverse N-protected bisphosphonic analogs of α-amino acids. As shown, the indirect formation of the corresponding phosphonium salt as a reactive intermediate during the conversion of 1-(N-acylamino)-1-ethoxyphosphonate into a 1-aminobisphosphonate derivative is a crucial component of the developed methodology.     

Copper‐Assisted/Copper‐Free Synthesis of Functionalized Dibenzo[b,f]oxepins and Their Analogs via a One‐Pot Tandem Reaction

A simple, convenient, and efficient method for the formation of functionalized dibenzo[b,f]oxepins and their analogs bearing both electron‐donating and electron‐withdrawing groups has been developed via a one‐pot cascade reaction. Most starting materials are commercially available 2‐(2‐hydroxyphenyl)acetonitriles and 2‐haloarylaldehydes. The procedure makes use of Cs₂CO₃ as the base, and DMF as solvent under copper‐assisted/copper‐free conditions. The reaction has a comprehensive group tolerance for substrates. Most of the reactions were complete within 1 h in good‐to‐excellent yields, and the reaction temperatures were relatively low. The protocol could be scaled up to grams without lowering the yield. A reaction mechanism was also proposed.     

Kinetic regularities of the heat release during the reactions of aliphatic hydrocarbons with aqueous HNO3

The kinetics of the heat release during the reactions of aqueous HNO₃ withn-heptane andn-octadecane was studied. The kinetic regularities of the reactions of hydrocarbons C₇H₁₆−C₁₈H₃₈ with HNO₃ and the heats of the reactions were described. At all stages, except initial, the hydrocarbon reacts with NO₂ and nitric acid reproduces NO₂ in the reaction with NO. The accumulation of NO₂ results in the acceleration of the process. When the pressure of the hydrocarbon vapor is equilibrium, its reaction with NO₂ can also proceed in the gas phase. The contribution of this reaction to the total heat release was estimated. The additives of aromatic and unsaturated hydrocarbons to aliphatic hydrocarbons increase strongly the initial rate of the heat release and changes slightly the subsequent stages of the process. Naphthenic hydrocarbons have almost no effect on the kinetic parameters of the process. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 35–40, January, 1998.     

Synthesis of Polysubstituted 1,4-Dihydropyridines via Four-component Reactions of Arylamine,Acetylenedicarboxylate, Aromatic Aldehyde and Ethyl Acetoacetate

An efficient synthetic protocol for the 1,4-diaryl-1,4-dihydropyridines was developed via the domino four-component reaction of arylamine, acetylenedicarboxylate, aromatic aldehyde and ethyl acetoacetate. The reaction mechanism involves the formation of β-enamino ester and its sequential Michael addition to arylidene acetoacetate.     

Single-electron transfer upon formation of 2,2,3,3-tetracyano-1-phenyl-7,8-dithiabicyclo[3.2.1]octane from allyl dithiobenzoate and tetracyanoethylene. Electrochemical investigations

Studies by the method of cyclic potential scanning from 0.2 to 1.9 V provided electroanalytical evidence that the reaction of allyl dithiobenzoate with tetracyanoethylene (TCNE) in MeCN proceeds as the reaction of the TCNE^.− radical anion with the PhSSAll^.+ radical cation to form phenyl-substituted 2,2,3,3-tetracyano-7,8-dithiabicyclo[3.2.1]octane. When current is not applied, the reaction does not proceed at 20°C for 3 days. However, this reaction in boiling MeCN occurs without electrochemical activation and, apparently, involves intermediate formation of the above radical ions. It was established by semiempirical PM3 calculations that allyl dithiobenzoate and TCNE form a stable charge-transfer complex that precedes chemical electron transfer. Dedicated to the memory of Professor Viktor Nikolaevich Drozd. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 78–81, January, 1999.     

A new strategy of tandem transetherification-intramolecular hetero Diels-Alder reaction with (E,Z)-mixture of ethyl 2-nitro-3-ethoxyacrylate and δ,ε-unsaturated alcohols leading to functionalized trans-fused bicyclic nitronates

Tandem reaction of (E,Z)-ethyl 2-nitro-3-ethoxyacrylate (E:Z=25:75) with δ,ε-unsaturated alcohols leading to functionalized trans-fused bicyclic nitronates as single stereoisomers in high yields has been developed under thermal condition and in the presence of a catalytic amount of a Lewis acid catalyst such as Yb(OTf)₃. This process involves the configurational control of transetherified intermediates under a rapid, reversible transetherification reaction pathway for affording stereoselective trans-fused cyclic nitronates as single stereoisomers in intramolecular hetero Diels-Alder reaction.     

Oxidative Diels-Alder reaction of 2, 5-dihydroxybenzoic acid with 1, 3-cyclopentadiene

The electrochemical oxidation of 2,5-dihydroxybenzoic acid (1) has been studied in the presence of 1,3-cyclopentadiene (2) as a diene in water/ethanol (40/60, v/v) mixture using cyclic voltammetry and controlled-potential coulometry. A plausible mechanism for the oxidation of 1 in the presence of 2 is presented. Compound 1 was converted into bis-adduct 5 via electrooxidation, Diels-Alder reaction of 2 to anodically generated 3,6-dioxocyclohexa-1,4-dienecarboxylic acid (1ox), decarboxylation reaction, electrooxidation and Diels-Alder reaction. The electrochemical synthesis of 5 was performed in a onepot reaction, without toxic reagents, at a carbon electrode in a simple cell using an environmentally friendly method.     

Synthesis of 6-Membered-Ring Fused Thiazine-Dicarboxylates and Thiazole-Pyrimidines via One-Pot Three-Component Reactions

A facile and efficient one-pot three-component reaction method for the synthesis of thiazine-dicarboxylates is reported. Reaction of an isocyanide and dialkyl acetylenedicarboxylate with 2-amino-4H-1,3-thiazin-4-one derivatives containing both an acidic proton and an internal nucleophile gave the products in good yields of 76–85%. The reactivity of dialkyl acetylenedicarboxylates was further tested in the synthesis of thiazole-pyrimidines where a two-component reaction of 2-aminothiazole with dialkyl acetylenedicarboxylates was successfully converted to a more efficient three-component reaction of a thiourea, α-haloketone and dialkyl acetylenedicarboxylate (DMAD/DEtAD) to give thiazole-pyrimidines in good yields of 70–91%.     

New and efficient conditions for the Z-selective synthesis of unsaturated esters by the Horner-Wadsworth-Emmons olefination

The Horner-Wadsworth-Emmons reaction of both 1 (Still's reagent) and 2 (Ando's reagent) with aldehydes was studied. Tris[2-(2-methoxyethoxy)ethyl]amine (TDA-1) was shown to be an efficient additive when the reaction was performed in THF at −78 °C. Selectivities close to 95% were obtained in the condensation of 1 with aromatic aldehydes. The use of a 5-fold excess of 18C6 in this reaction had already been reported. However, we have defined conditions in which only catalytic amounts are required.     

Mukaiyama aldolisation reactions of α,β-epoxyaldehydes in aqueous media

The Mukaiyama aldolisation reaction in aqueous media of cis and trans α,β-epoxyaldehydes with tert-butyldimethylsilyl ketene acetal in the presence of Lewis's acids was studied. Sc(OTf)₃ gave the best results in terms of selectivity. The same reaction of cis and trans α,β-epoxyaldehydes with the enoxysilane of ethyl pyruvate resulted in epoxy substituted ulosonic derivatives issued from a double sequential condensation of the pyruvate on the epoxy derivatives.     

Chip-Based Spectrofluorimetric Determination of Iodine in a Multi-Syringe Flow Platform with and without In-Line Digestion—Application to Salt,Pharmaceuticals, and Algae Samples

In this work, a flow-based spectrofluorimetric method for iodine determination was developed. The system consisted of a miniaturized chip-based flow manifold for solutions handling and with integrated spectrofluorimetric detection. A multi-syringe module was used as a liquid driver. Iodide was quantified from its catalytic effect on the redox reaction between Ce(IV) and As(III), based on the Sandell–Kolthoff reaction. The method was applied for the determination of iodine in salt, pharmaceuticals, supplement pills, and seaweed samples without off-line pre-treatment. An in-line oxidation process, aided by UV radiation, was implemented to analyse some samples (supplement pills and seaweed samples) to eliminate interferences and release iodine from organo-iodine compounds. This feature, combined with the fluorometric reaction, makes this method simpler, faster, and more sensitive than the classic approach of the Sandell–Kolthoff reaction. The method allowed iodine to be determined within a range of 0.20–4.0 µmol L⁻¹, with or without the in-line UV digestion, with a limit of detection of 0.028 µmol L⁻¹ and 0.025 µmol L⁻¹, respectively.     

Development of radical addition-cyclization-elimination reaction of oxime ether and its application to formal synthesis of (±)-martinelline

Radical addition-cyclization-elimination (RACE) reaction of oxime ether carrying unsaturated ester provides a novel method for the construction of pyrroloquinoline. Treatment of oxime ethers with Bu₃SnH and AIBN gave N-norpyrroloquinoline as a major product, which was also obtained by the radical reaction of the corresponding hydrazone and imine. The radical reaction of aldehyde and ketone carrying unsaturated ester proceeded stereoselectively to give cis-furoquinolines and cis-hydroxyesters. The RACE reactions by using each of Bu₃SnNMe₂, Bu₃SnD, and/or D₂O were also examined in order to propose a reaction pathway to N-norpyrroloquinoline. Furthermore, the synthetic utility of RACE reaction is demonstrated by preparation of a key intermediate for the synthesis of (±)-martinelline.     

噻二唑衍生物对银的缓蚀性能研究

本文研究了主要成分为5-甲基-2-戊基二硫代-1,3,4-噻二唑的复配型缓蚀剂TSJ-T6,在浓度为5.0×10-5g/g的H2S中对银的缓蚀性能。通过增重实验、接触角分析、电化学极化曲线测试以及分子动力学模拟研究了该缓蚀剂的缓蚀效率及缓蚀机理。增重实验结果证明,缓蚀剂TSJ-T6对银片在H2S中的腐蚀具有良好的缓蚀效果,缓蚀剂浓度为2.5×10-5g/g时,缓蚀效率高达94.51%。接触角分析结果表明,该缓蚀剂分子在银片和腐蚀液的界面形成了一层疏水保护膜。极化曲线结果表明,缓蚀剂TSJ-T6的存在降低了阴、阳极的塔菲尔斜率,为混合型缓蚀剂;同时,该缓蚀剂的存在显著降低了腐蚀电流密度,表明该缓蚀剂对银片在H2S中的腐蚀有良好的缓蚀效果。分子动力学模拟表明,缓蚀剂分子通过噻二唑环和链上的硫、氮原子吸附在银表面,烷基链则以一定角度指向溶液。     

Synthesis of the [11]Cyclacene Framework by Repetitive Diels–Alder Cycloadditions

The Diels–Alder cycloaddition between bisdienes and bisdienophile incorporating the 7-oxa-bicyclo[2.2.1]heptane unit are well known to show high diastereoselectivity that can be exploited for the synthesis of molecular belts. The related bisdiene 5,6,7,8-tetramethylidene-2-bicyclo[2.2.2]octene is a valuable building block for the synthesis of photoprecursors for acenes, but it has not been employed for the synthesis of molecular belts. The present work investigates by computational means the Diels–Alder reaction between these bisdiene building blocks with syn-1,4,5,8-tetrahydro-1,4:5,8-diepoxyanthracene, which shows that the diastereoselectivity of the Diels–Alder reaction of the etheno-bridged bisdiene is lower than that of the epoxy-bridged bisdiene. The reaction of the etheno-bridged bisdiene and syn-1,4,5,8-tetrahydro-1,4:5,8-diepoxyanthracene in 2:1 ratio yields two diastereomers that differ in the orientation of the oxa and etheno bridges based on NMR and X-ray crystallography. The all-syn diastereomer can be transformed into a molecular belt by inter- and intramolecular Diels–Alder reactions with a bifunctional building block. The molecular belt could function as a synthetic intermediate en route to a [11]cyclacene photoprecursor.     

Towards Stereoselective Synthesis of the C(31)–C(39) and C(20)–C(27) Fragments of Phorboxazole A

The stereoselective synthesis of the C(31)–C(39) and C(20)–C(27) fragments of phorboxazole A ( 1 ) was achieved from commercially available and inexpensive D ‐mannitol. Crimmins aldol reaction and a decarboxylative Claisen‐type reaction are the key steps for the C(31)–C(39) fragment, and L ‐proline‐catalyzed aldol reaction, Sharpless asymmetric epoxidation, and epoxide ring opening reaction with Gilman's reagent are the key steps for the C(20)–C(27) fragment of phorboxazole.     

Determination of 2-Acetyl-1-pyrroline via a Color-Change Reaction Using Chromium Hexacarbonyl

At present, there is no colorimetric method for the quantitation of the aroma compound 2-acetyl-1-pyrroline (2AP). A novel colorimetric method was developed for the determination of 2AP content using chromium hexacarbonyl (Cr(CO)₆) as a reagent. The reaction of synthetic 2AP with chromium hexacarbonyl reagent solution in the presence of light produced a green product with an absorption maximum (λ_max) at 623 nm. GC–MS was used to confirm the color-change reaction, which showed the loss of 2AP after the addition of Cr(CO)₆. This novel method enables facile and cost-effective determination of 2AP in fragrant rice. A comparative analysis of fragrant and nonfragrant rice grain extracts showed that no color-change reaction occurred with the nonfragrant rice sample. A limit of detection (LOD) of 2.00 mg L⁻¹ was determined by method validation with an effective linear concentration ranging from 5.00 to 60.00 mg L⁻¹ of 2AP. The results obtained using the developed colorimetric method were consistent with those obtained by automated static headspace gas chromatography with nitrogen-phosphorus detection (SHS-GC–NPD).