芳基-芳基偶联反应的研究进展

综述了近年来芳基-芳基偶联反应的研究进展, 包括不同类型芳基-芳基偶联反应的特点、机理和应用, 尤其是对立体选择性和区域选择性的偶联方法进行了重点介绍.     

芳基膦（肿）酸及其盐的合成,结构与倍频效应研究

本文基于将无机非线性光学材料的有效基团（畸变阴离子基团）及有机共轭体系结合为一体的设想，用改进的Ｄｏａｋ－Ｆｒｅｅｄｍａｎ法合成了一系列芳基膦（胂）酸及其盐共２５个化合物，讨论了分子的电子性质及其在晶体中的排列方式。实验结果表明，在这类化合物的分子内存在着一定的电荷转移；对甲苯膦酸的晶体结构分析表明，分子间存在着氢键作用，使分子呈二聚的排列方式。在所合成的化合物中，有６种表现出宏观倍频效应。     

芳基丙酮酸及其乙酯的合成

α-甲酰氨基-β-芳基丙烯酸乙酯用5％盐酸乙醇溶液水解生成相应的芳基丙酮酸乙酯,再经碱处理变为相应的芳基丙酮酸。     

芳基亚磺酸钠自身偶联合成二芳基砜

在二价铜促进下,芳基亚磺酸钠通过分子间脱硫,发生自身偶联,高选择性高产率地合成了对称性的二芳基砜类化合物。反应无需惰性气体保护,条件温和,具有良好的官能团耐受性,可以用于二芳基砜衍生物的高效合成。     

醋酸铜促进的芳基磺酰肼自身偶联合成二芳基砜

研究了一种新颖的醋酸铜促进的芳基磺酰肼的自身偶联反应.该反应通过分子间脱硫和脱氮的过程,高选择性高产率的合成对称的二芳基砜类化合物.该反应中溶剂对反应的副产物的产生有十分显著的影响.反应无需惰性气体保护,具有良好的官能团耐受性,硝基、卤素等官能团及杂环体系都对反应无明显影响.该合成方法可以用于治疗麻风病的药物氨苯砜的制备.     

Two New Diarylheptanoids from the Rhizomes of Zingiber officinale

Two new diaryheptanoids, (5S)-5-acetoxy-l,7-bis(4-hydroxy-3-methoxyphenyl)-3-heptanone (1) and (3S,SS)-3,5-diacetoxy-l,7-bis(4-hydroxy-3-methoxyphenyl)heptane (2) wereisolated from the rhizomes of Zingiber officinale. Their structures were elucidated by spectralmethods.     

α-氯汞代乙醛与芳基重氮盐的反应

α-氯汞代乙醛与芳基重氮盐在铜盐存在下反应,生成氯化芳基汞,用这种方法合成了12种氯化芳基汞,这可能是一种自由基反应。     

2-[1-芳酰基-1-(芳基偶氮) 亚甲基] 苯并噻唑啉的合成

本实验通过2-(1-芳甲酰基亚甲基)苯并噻唑啉和芳基重氮盐反应, 高产率地制得一系列2-[1-芳酰基-1-(芳基偶氮)亚甲基]苯并噻唑啉。     

芳基离子及芳基自由基与 环己二烯离子及环己二烯自由基的区别

通过比较芳香亲电取代与芳基重氮盐的水解反应和芳香亲核取代与芳基金属有机试剂参与的反应中芳香部分结构的差别来说明芳基正离子与环己二烯正离子以及芳基负离子与环己二烯负离子的区别。讨论了芳香自由基偶联中的芳基自由基及其对芳香环的自由基加成中的环己二烯自由基的差别。还讨论了芳基离子和自由基结构与芳香性的关系。反应中涉及芳烃芳香环碳原子的sp2杂化轨道形成的σ键断裂时,苯环的6电子大π键不被破坏,根据电子转移的情况,可以形成芳基正离子、芳基负离子或芳基自由基。而亲电试剂、亲核试剂或自由基对芳烃的苯环π键发生的加成反应,都会破坏苯环的6电子大π键,使其失去芳香性,相应地形成环己二烯正离子、环己二烯负离子和环己二烯自由基中间体。     

Synthesis and spectroscopy of N3P3X5OCH=CH2 (X = Cl, F, OCH3, OCH2CF3, N(CH3)2) and N3P3X4(OCH=CH2)2 (X = Cl, N(CH3)2). Correlations of ultraviolet photoelectron spectroscopy and nuclear magnetic resonance data to electronic and geometrical structure

The syntheses of the vinyloxycyclotriphosphazene derivatives N3P3X5OCH=CH2 (X = OMe, OCH2CF3) and the N3P3(NMe2)4(OCH=CH2)2 isomeric mixture along with improved preparations of N3P3X5OCH=CH2 (X = F, NMe2) are reported. The interactions between the vinyloxy function and the cyclophosphazene in these and the previously reported N3P3Cl5 (OCH=CH2) and N3P3F6-n(OCH=CH2)n (n = 1-4) have been examined by ultraviolet photoelectron spectroscopy (UPS) and NMR spectroscopy. The UPS data for the chloro and fluoro derivatives show a strong electron-withdrawing effect of the phosphazene on the olefin that is mediated with decreasing halogen substitution. The 1H and 13C NMR data for N3P3X5OCH=CH2 (X = F, Cl, OMe, OCH2CF3, NMe2) show significant changes as a function of the phosphazene substituent. There is a linear correlation between the beta-carbon chemical shift on the vinyloxy unit and the phosphorus chemical shift at the vinyloxyphosphorus centers. The chemical shifts of the different phosphorus centers on each ring are also related in a linear fashion. These relationships may be understood in terms of the relative electron donor-acceptor abilities of the substituents on the phosphazene ring. The 1H NMR spectra of the N3P3(NMe2)4(OCH-CH2)2 isomeric mixture allow for assignment of the relative amounts of cis and trans isomers. A model for the observed cis preference in the formation of N3P3Cl4(OCH=CH)2 is presented.     

Fluorinated bismuth alkoxides: from monomers to polymers and oxo-clusters

A series of new bismuth fluoroalkoxide compounds have been prepared through the treatment of 1,1,1,3,3,3-hexafluoro-2-propanol with BiAr3 (where Ar=Ph, p-Tol). Reactions were conducted without the use of any additional solvent and the reaction products distilled or extracted with non-polar or polar Lewis base solvents. Structural analyses reveal that under variable reaction conditions the interaction of BiAr3 with (CF3)2CHOH can give a mixture of bismuth complexes with varying degrees of substitution, cluster formation and aggregation. Compounds [Bi(OCH(CF3)2)3(pyr)2] () (pyr=pyridine), [Bi(OCH(CF3)2)3(thf)3] () (thf=tetrahydrofuran), [Bi2(OCH(CF3)2)3(dabco)3] () (dabco=1,4-diazabicyclo[2.2.2]octane), [PhBi(OCH(CF3)2)2]n (), [Bi2O(OCH(CF3)2)4(C7H8)]2 () (C7H8=toluene), [Bi9O7(OCH(CF3)2)13] (), [Bi2O(OCH(CF3)2)4(Et2O)]2 (), [Bi2O(OCH(CF3)2)4(thf)]2 () and [Bi2O(OCH(CF3)2)4(tmeda)2] () (tmeda=N,N,N',N'-tetramethylethylenediamine) have been fully characterised including by single crystal X-ray diffraction.     

1R,3S-1,2,2-三甲基-1,3-环戊二胺为配体的铂髤配合物的合成、表征和抗肿瘤活性

本文合成了9种含有由天然D( )鄄樟脑衍生的1R,3S鄄1,2,2鄄三甲基鄄1,3鄄环戊二胺(A)为配体的铂髤配合物[Pt髤AX]{其中,X=(CH2)3C(COO-)2(1,1鄄环丁烷二羧酸根),2CH3OCH2COO-,2CH3CH2OCH2COO-,2CH3(CH2)3OCH2COO-,[OCH(CH3)COO]2-(乳酸根),(OCH2COO)2-(乙醇酸根),2CH3OCH2CH2OCH2COO-,2CH3CH2OCH2CH2OCH2COO-和2CH3(CH2)3OCH2CH2OCH2COO-}。通过元素分析、热重分析、红外光谱、1H核磁共振谱和电喷雾质谱等对配合物进行了表征。体外生物活性测试表明,部分配合物对A549人肺癌细胞和HCT鄄116人结肠癌细胞具有较强的抗肿瘤活性。     

Gas-phase reactivity of the O=P(OCH3)2+ phosphonium ion with aliphatic esters in a quadrupole ion trap. Spontaneous elimination of ketenes

Ion-molecule reactions between the O=P(OCH(3))(2) (+) phosphonium ions and five aliphatic esters (methyl acetate, methyl propionate, methyl 2-methylpropionate, methyl butyrate and ethyl acetate) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH(3))(2) (+) phosphonium ions, formed by electron ionization from neutral trimethyl phosphite, were found to react with aliphatic esters to give an adduct ion [RR'CHCOOR", O=P(OCH(3))(2)](+), which loses spontaneously a molecule of ketene CH(2)=CO or substituted ketenes RR'C=CO. Isotope-labeled methyl acetate was used to elucidate fragmentation mechanisms. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH(3))(2) (+) and methyl acetate is described.     

Synthesis and Crystal Structure of FeCo_2(CO)_8(μ_3-S)〔P(OCH_2Ph)_3〕

1INTRODUCTIONBytreatingFeCo2(CO),(p,-S)withgroupVligands[L=PPh,,AsPh,,PBus",p(OEt),j,monosubstitutedderivativesFeCo2(CO),(p,-S)(L)havebeenobtained{1'2i.13C-NMRshowedthatthereplacementofCObyagroupVligandinFeCo,(CO),(p,-S)isatonecobaltatominthemonosubstitutedderivativet2).How-ever,thesubstitutedderivativeofFeCo,(CO),(p,-S)withP(OCH,Ph),hasnotbeenreportedanditscrystalstructurehasnotbeendetermined.WehavesynthesizedthetitlecompoundFeCo,(CO),(p,-S)[P(OCH,Ph),jandtestifiedth…     

Comparison of hydrogen- and halogen-bonding interactions in the complexes of the substituted carbonyl compounds with hypohalous acids and monohaloamines

Structural Chemistry - An ab initio study of the complexes formed by hypohalous acids and monohaloamines (designated as HAX where A = O or NH and X = Cl, Br, or I) with RCHO (R = H, CH3, OCH3, and...     

Ring-closing metathesis reactions of terminal alkene-derived cyclic phosphazenes

The first examples of ring-closing metathesis (RCM) reactions of a series of terminal alkene-derived cyclic phosphazenes have been carried out. The tetrakis-, hexakis-, and octakis(allyloxy)cyclophosphazenes (NPPh(2))(NP(OCH(2)CH=CH(2))(2))(2) (1), N(3)P(3)(OCH(2)CH=CH(2))(6) (2), and N(4)P(4)(OCH(2)CH=CH(2))(8) (3) and the tetrakis(allyloxy)-S-phenylthionylphosphazene (NS(O)Ph)[NP(OCH(2)CH=CH(2))(2)](2) (4) were prepared by the reactions of CH(2)=CHCH(2)ONa with the cyclophosphazenes (NPPh(2))(NPCl(2))(2), N(3)P(3)Cl(6), and N(4)P(4)Cl(8) and the S-phenylthionylphosphazene (NS(O)Ph)(NPCl(2))(2). The reactions of 1-4 with Grubbs first-generation olefin metathesis catalyst Cl(2)Ru=CHPh(PCy(3))(2) resulted in the selective formation of seven-membered di-, tri-, and tetraspirocyclic phosphazene compounds (NPPh(2))[NP(OCH(2)CH=CHCH(2)O)](2) (5), N(3)P(3)(OCH(2)CH=CHCH(2)O)(3) (6), and N(4)P(4)(OCH(2)CH=CHCH(2)O)(4) (7) and the dispirocyclic S-phenylthionylphosphazene compound (NS(O)Ph)[NP(OCH(2)CH=CHCH(2)O)](2) (8). X-ray structural studies of 5-8 indicated that the double bond of the spiro-substituted cycloalkene units is in the cis orientation in these compounds. In contrast to the reactions of 1-4, RCM reactions of the homoallyloxy-derived cyclophosphazene and thionylphosphazene (NPPh(2))[NP(OCH(2)CH(2)CH=CH(2))(2)](2) (9) and (NS(O)Ph)[NP(OCH(2)CH(2)CH=CH(2))(2)](2) (10) with the same catalyst resulted in the formation of 11-membered diansa compounds NPPh(2)[NP(OCH(2)CH(2)CH=CHCH(2)CH(2)O)](2) (11) and (NS(O)Ph)[NP(OCH(2)CH(2)CH=CHCH(2)CH(2)O)](2) (13) and the intermolecular doubly bridged ansa-dibino-ansa compounds 12 and 14. The X-ray structural studies of compounds 11 and 13 indicated that the double bonds of the ansa-substituted cycloalkene units are in the trans orientation in these compounds. The geminal bis(homoallyloxy)tetraphenylcyclotriphosphazene [NPPh(2)](2)[NP(OCH(2)CH(2)CH=CH(2))(2)] (15) upon RCM with Grubbs first- and second-generation catalysts gave the spirocyclic product [NPPh(2)](2)[NP(OCH(2)CH(2)CH=CHCH(2)CH(2)O)] (16) along with the geminal dibino-substituted dimeric compound [NPPh(2)](2)[NP(OCH(2)CH(2)CH=CHCH(2)CH(2)O)(2)PN][NPPh(2)](2) (17) as the major product. The dibino compound 17, upon reaction with the Grubbs second-generation catalyst, was found to undergo a unique ring-opening metathesis reaction, opening up the bino bridges and partially converting to the spirocyclic compound 16.     

Dehydration reaction of hydroxyl substituted alkenes and alkynes on the Ru(2)S(2) complex

A variety of inter- and intramolecular dehydration was found in the reactions of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)(mu-S(2))](CF(3)SO(3))(4) (1) with hydroxyl substituted alkenes and alkynes. Treatment of 1 with allyl alcohol gave a C(3)S(2) five-membered ring complex, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)CH(2)CH(OCH(2)CH=CH(2))S]](CF(3)SO(3))(4) (2), via C-S bond formation after C-H bond activation and intermolecular dehydration. On the other hand, intramolecular dehydration was observed in the reaction of 1 with 3-buten-1-ol giving a C(4)S(2) six-membered ring complex, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2) [mu-SCH(2)CH=CHCH(2)S]](CF(3)SO(3))(4) (3). Complex 1 reacts with 2-propyn-1-ol or 2-butyn-1-ol to give homocoupling products, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCR=CHCH(OCH(2)C triple bond CR)S]](CF(3)SO(3))(4) (4: R = H, 5: R = CH(3)), via intermolecular dehydration. In the reaction with 2-propyn-1-ol, the intermediate complex having a hydroxyl group, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH=CHCH(OH)S]](CF(3)SO(3))(4) (6), was isolated, which further reacted with 2-propyn-1-ol and 2-butyn-1-ol to give 4 and a cross-coupling product, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH=CHCH(OCH(2)C triple bond CCH(3))S]](CF(3)SO(3))(4) (7), respectively. The reaction of 1 with diols, (HO)CHRC triple bond CCHR(OH), gave furyl complexes, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SSC=CROCR=CH]](CF(3)SO(3))(3) (8: R = H, 9: R = CH(3)) via intramolecular elimination of a H(2)O molecule and a H(+). Even though (HO)(H(3)C)(2)CC triple bond CC(CH(3))(2)(OH) does not have any propargylic C-H bond, it also reacts with 1 to give [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)C(=CH(2))C(=C=C(CH(3))(2))]S](CF(3)SO(3))(4) (10). In addition, the reaction of 1 with (CH(3)O)(H(3)C)(2)CC triple bond CC(CH(3))(2)(OCH(3)) gives [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(2)][mu-S=C(C(CH(3))(2)OCH(3))C=CC(CH(3))CH(2)S][Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)]](CF(3)SO(3))(4) (11), in which one molecule of CH(3)OH is eliminated, and the S-S bond is cleaved.     

Syntheses of ketonated disulfide-bridged diruthenium complexes via C-H bond activation and C-S bond formation

The alpha-C-H bonds of 3-methyl-2-butanone, 3-pentanone, and 2-methyl-3-pentanone were activated on the sulfur center of the disulfide-bridged ruthenium dinuclear complex [(RuCl(P(OCH3)3)2)2(mu-S2)(mu-Cl)2] (1) in the presence of AgX (X = PF6, SbF6) with concomitant formation of C-S bonds to give the corresponding ketonated complexes [(Ru(CH3CN)2(P(OCH3)3)2)(mu-SSCHR1COR2)(Ru(CH3CN)3(P(OCH3)3)2)]X3 ([5](PF6)3, R1 = H, R2 = CH(CH3)2, X = PF6; [6](PF6)3, R1 = CH3, R2 = CH2CH3, X = PF6; [7](SbF6)3, R1 = CH3, R2 = CH(CH3)2, X = SbF6). For unsymmetric ketones, the primary or the secondary carbon of the alpha-C-H bond, rather than the tertiary carbon, is preferentially bound to one of the two bridging sulfur atoms. The alpha-C-H bond of the cyclic ketone cyclohexanone was cleaved to give the complex [(Ru(CH3CN)2(P(OCH3)3)2)(mu-SS-1- cyclohexanon-2-yl)(Ru(CH3CN)3(P(OCH3)3)2)](SbF6)3 ([8](SbF6)3). And the reactions of acetophenone and p-methoxyacetophenone, respectively, with the chloride-free complex [(Ru(CH3CN)3(P(OCH3)3)2)2(mu-S2)]4+ (3) gave [(Ru(CH3CN)2(P(OCH3)3)2)(mu-SSCH2COAr)(Ru(CH3CN)3(P(OCH3)3)2)](CF3SO3)3 ([9](CF3SO3)3, Ar = Ph; [10](CF3SO3)3, Ar = p-CH3OC6H4). The relative reactivities of a primary and a secondary C-H bond were clearly observed in the reaction of butanone with complex 3, which gave a mixture of two complexes, i.e., [(Ru(CH3CN)2(P(OCH3)3)20(mu-SSCH2COCH2CH3)(Ru(CH3CN)3(P(OCH3)3)2)](CF3SO3)3 ([11](CF3SO3)3) and [(Ru(CH3CN)2(P(OCH3)3)2)(mu-SSCHCH3COCH3)(Ru(CH3CN)3(P(OCH3)2)](CF3SO3)3 ([12](CF3SO3)3), in a molar ratio of 1:1.8. Complex 12 was converted to 11 at room temperature if the reaction time was prolonged. The relative reactivities of the alpha-C-H bonds of the ketones were deduced to be in the order 2 degrees > 1 degree > 3 degrees, on the basis of the consideration of contributions from both electronic and steric effects. Additionally, the C-S bonds in the ketonated complexes were found to be cleaved easily by protonation at room temperature. The mechanism for the formation of the ketonated disulfide-bridged ruthenium dinuclear complexes is as follows: initial coordination of the oxygen atom of the carbonyl group to the ruthenium center, followed by addition of an alpha-C-H bond to the disulfide bridging ligand, having S=S double-bond character, to form a C-S-S-H moiety, and finally completion of the reaction by deprotonation of the S-H bond.     

Intramolecular amine-induced [1,3]-sigmatropic rearrangement in the reactions of aminophosphinites or phosphites with elemental sulfur or selenium

Ether- and thioether-functionalized cyclodiphosphazanes cis-[tBuNP(OCH2CH2EMe)]2 (E = O, 1; E = S, 2) react with 2 equiv of elemental sulfur or selenium to produce dichalcogenides cis-[tBuNP(E)(OCH2CH2EMe)]2 (4-6), whereas the similar reaction of amine-functionalized cyclodiphosphazane cis-[tBuNP(OCH2CH2NMe2)]2 (3) with elemental chalcogen results in the formation of thio- or selenophosphates trans-[tBuNP(O)(ECH2CH2NMe2)]2 (E = S, 7; E = Se, 8) through [1,3]-sigmatropic rearrangement. The X-ray crystal structure of 8 confirms the rearranged product as the trans isomer with a planar P2N2 ring. The equimolar reaction of P(OCH2CH2OMe)3 (9) with elemental sulfur or selenium produces the simple sulfide and selenide E=P(OCH2CH2OMe)3 (E = S, 11; E = Se, 12) derivatives, respectively. In contrast, the reaction between P(OCH2CH2NMe2)3 (10) and S or Se furnishes the rearranged products (13 and 14). The rearrangement reaction was monitored by (31)PNMR spectroscopy, which confirms the formation of selenophosphinic acid as the first step of the rearrangement. The [1,3]-sigmatropic rearrangement presumably takes place through chalcogen-nitrogen interactions.