外式双环[2.2.1]庚烷(庚-5-烯)-2,3-二甲酸酐膦二肽衍生物的合成

选择有机磷基团对斑蝥素的结构骨架进行修饰改造,以外式双环[2.2.1]庚-5-烯-2,3-二甲酸酐为原料,设计合成了一系列斑蝥素类似物。化合物的结构经1HNMR,MS及元素分析确证。     

Metathesis of spirocyclo[2.2.1]hept-2-ene-7,1'-cyclopropane

Metathesis of spirocyclo[2.2.1]hept-2-ene-7,1'-cyclopropane and its co-metathesis with norbornene and 5-decene on homogeneous and heterogeneous catalytic systems were carried out for the first time. The reactions were shown to proceed with retention of the spirosystem.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 138–139, January, 1993.     

氮杂炔正离子与环烯反应的机理及取代基效应

用DFT方法研究了氮杂炔正离子[R-C≡N-CH3] 与二环[2,2,1]-2-庚烯的反应机理。所有几何构型用B3LYP/6-31G**基组进行优化,过渡态通过振动分析和内聚反应坐标进行了确认。并在相同基组上研究了当R为不同取代基时的反应变化规律。结果表明该反应为环加成反应,有两条反应途径,产物主要通过能量较低的过渡态TSa生成。当取代基为支链烷烃基团时,反应位垒较大;取代基为直链烷烃基团和苯环时,反应较易进行。     

Reaction of 2-azabicyclo[2.2.1]heptenes with nitrile oxides

The reaction of 2-azanorbornene derivatives with nitrile oxides (generated in situ by dehydrohalogenation of N-hydroxyimoyl halides) affords two regioisomers with the exo-arrangement of the isoxazoline ring.     

2,3-二羧基-双环[2.2.1]2,5-庚二烯价键异构化反应的研究

以聚四苯基卟啉(P-TPP)为敏化剂,研究了2,3-二羧基-双环[2.2.1]-2,5-庚二烯(N)的光化学价键异构化反应,在0.1mol/L的碳酸钠甲醇溶剂中,在适量的P-TPP存在下,可见光照射时,N可以定量地转化为2,3-二羧基四环[2.2.1.0^2,6.0^3,5]庚烷(Q),Q在聚四苯基卟啉钴络合物(Co-P-TPP)催化剂的作用下,又可定量地异构化返回N.分别研究了敏化剂和催化剂用量对反应的影响。通过反应物之间激发态能量的比较及N对P-TPP荧光的猝灭试验,证明光异构化反应是通过电子转移反应机制进行的。     

Photoelectron spectra and quantum-chemical calculation of 5-vinyl- and 5-ethylidenebicyclo[2.2.1]hept-2-ene

The photoelectron spectra of 5-vinyl- and 5-ethylidenebicyclo[2.2.1]-hept-2-ene have been measured, and they have been interpreted with the aid of a quantumchemical calculation by the CNDO/S method. The reactivity of the compounds indicated has been discussed on the basis of the results obtained.Translated from Teoreticneskaya i Éxperimental'naya Khimiya, Vol. 21, No. 4, pp. 472–475, July–August, 1985.     

Stereochemical dependence of13C-shift and31P-13C-coupling in 3-substituted bicyclo[2.2.1]hept-5-en-2-yl- and bicyclo[2.2.2]oct-5-en-2-yl-phosphonates

Steric influences operating on¹³C-shifts and³¹P-¹³C-coupling constants have been investigated on phosphonates with a rigid framework.

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Stereochemische Abhängigkeit von¹³C-Verschiebungen und³¹P-¹³C-Kopplungskonstanten in 3-substituierten Bicyclo[2.2.1]hept-5-en-2-yl- und Bicyclo[2.2.2]oct-5-en-2-yl-phosphonaten

Zusammenfassung Der sterische Einfluß auf¹³C-Verschiebungen und³¹P-¹³C Kopplungskonstanten wurde an Phosphonaten mit starrer Struktur untersucht.

     

Desymmetrization of meso 7-aza-2,3-bis(phenylsulfonyl) bicyclo[2.2.1]hept-2-ene: a re-examination. Kinetic resolution of racemic 3-arylsulfonyl-7-aza-2-bromobicyclo[2.2.1]hepta-2,5-dienes

The inexpensive large scale preparation of N-methoxycarbonyl-7-aza-2,3-bis(phenylsulfonyl)bicyclo[2.2.1]hept-2-ene and the re-examination of its stereoselective desymmetrization are reported. Moreover, the kinetic resolution of N-protected 3-arylsulfonyl-7-aza-2-bromobicyclo[2.2.1]hepta-2,5-dienes promoted by (R,R)-hydrobenzoin is described, representing a new tool to fix the absolute stereochemistry of the 7-azabicyclo[2.2.1] skeleton.     

The Non-planarity of the Bicyclo[2.2.1]hept-2-ene Double bond. Crystal Structures of Bicyclo[2.2.2]oct-2-ene,Bicyclo[2.2.1]hept-2-ene,and Bicyclo[2.1.1]hex-2-ene Systems

The crystal structures of (1R,4R,5S,8S)-9,10-dimethylidentricyclo[6.2.1.0^2,7]undec2(7)-ene-4,5-dicarboxylic anhydride ( 3 ), (1R,4R,5S,8S)11-isopropylidene-9,10-dimethylidenetricyclo[6.2.1.m^2,7]undec-2(7)-ene-4,5-dicarboxylic anhydride ( 6 ), (1R,4R,5S8S)-9,10-dimethylidenetricyclo[6.2.2.0^2,7]dodec-2(7)-ene-4,5-dicarboxylic anhydride ( 9 ), (1R4R5S8S)-TRICYCLO[6.2.2.0^2,7]dodeca-2(7), 9-diene-4,5-dicarboxylic anhydride ( 12 ) and (4R,5S)-tricyclo[6.1.1.0^2.7]dec-2(7)-ene-4,5-dicarboxylic acid ( 16 ) were established by X-ray diffraction. The alkyl substituents onto the endocyclic bicyclo[2.2.1]hept-2-ene double bond deviate from the C(1), C(2), C(3), C(4), plane by 13.5°4 in 3 and by 13.9° in 6 , leaning toward the endo-face. No such out-of-plane deformations were observed with the bicyclo[2.2.2]oct-2-ene derivatives 9 and 12 . The exocyclic s-cis-butadiene moieties in 3, 6 and 9 do not deviate significantly from planarity. The deviation from planarity of the double bond n bicyclo[2.2.1]hept-2-ene derivatives and planarity in bicyclo[2.2.2]oct-2-ene analogues is shown to be general by analysis of all known structures in the Cambridge Crystallographic Data File. The non-planarity of the bicyclo[2.2.1]hept-2-ene double bond cannot be attributed only to bond-angle deformations which would favour rehybridizatoin of the olefinic C-atoms since the double bond in the more strained bicyclo[2.1.1]hex-2-ene drivative 16 deviates from planarity by less than 4°.     

Reaction and sensing of octafluorocyclopentene with 1,5-diazabicyclo[4,3,0]non-5-ene

Reactions of octafluorocyclopentene (C₅F₈) with 1,5-diazabicyclo[4,3,0]non-5-ene (DBN) are studied by analyses of an isolated product and optical spectra from the viewpoint of applications to gas-sensors. Obtained results suggest that nucleophilic reactions of DBN proceed toward the double bond of C₅F₈ molecule accompanied with hydroxide anion attack on carbon-fluoride bonds of C₅F₈ moiety under ambients, forming unique C₅F₈-modified adducts. The present reaction is conducive to a new type of technologies for quick and selective sensing that can be used to develop alarm systems in the field of the environment and etching processing factories.     

Addition of bromine to 2-methyl-2-azabicyclo[2.2.1]hept-5-ene

Addition of bromine to 2-methyl-2-azabicyclo[2.2.1]hept-5-ene was studied. Unexpectedly, 3-bromo-1-methyl-1-azoniatricyclo[2.2.1.0^2,6]heptane tribromide was isolated rather than the product of bromine addition to the double bond. The former reacted with the starting alkene in a polar solvent to form the corresponding monobromide.     

Synthesis and free radical polymerization of 2-methylene-7-oxabicyclo[2.2.1]heptane

A new monomer, 2-methylene-7-oxabicyclo[2.2.1]heptane ( IV ) was synthesized via four steps. Its structure was confirmed by IR, ¹H-NMR, and ¹³C-NMR spectra as well as elementary analysis. Free radical polymerization and copolymerization of IV were investigated. No homopolymer was obtained due to the effect of allyl inhibition. When IV copolymerized with electron-donor monomers, such as vinyl acetate and stvrene, IV acted as inhibitor for the polymerization of vinyl acetate, but could not inhibit the polymerization of styrene. However, the copolymers of IV with electron-accepting monomers, such as methyl methacrylate, acrylonitrile, or maleic anhydride (MA) were obtained. The contents of IV in the copolymers increased as e values of electron-accepting monomers increased. Strictly alternating copolymer was obtained only in the case of MA and IV . The thermal properties of copolymers were investigated. © 1995 John Wiley & Sons, Inc.     

W(II)-catalyzed hydroarylation of bicyclo[2.2.1]hept-2-ene by simple arenes

The tungsten(II) carbonyl compound (CO)₄W(μ-Cl)₃W(SnCl₃)(CO)₃ has been found to be a very effective catalyst for the hydroarylation of bicyclo[2.2.1]hept-2-ene (norbornene) conducted in arene solution at room temperature. Norbornene adducts with benzene, toluene, para-xylene, and mesitylene have been isolated and their structures have been unambiguously established by means of ¹H and ¹³C NMR spectroscopy. On the basis of ¹H NMR monitoring of several catalytic reactions, a possible mechanism involving coordination of norbornene to the W(II) atom and its activation has been proposed.     

Synthesis and Characterization of New Chalcone Derivatives from cis-Bicyclo[3.2.0]hept-2-en-6-one

A series of chalcone derivatives (3a–k) were prepared via the reaction of cis-bicyclo[3.2.0]hept-2-en-6-one (1) with the respective arylaldehydes (2a–k) and were then characterized by Fourier transform infrared (FT-IR), ¹H NMR, ¹³C NMR, and elemental analyses.     

对映体纯1-甲基-7-氧杂双环[2.2.1]庚烷-2-酮的制备

1-甲基 - 7-氧杂双环 [2 .2 .1 ]庚烷 - 2 -酮 ( 1 )是萜类天然产物全合成中的重要中间体 ,能被广泛地应用于多种桉烷 ( Eudesmane)、沉香呋喃 ( Agarofuran)和降胡萝卜素 ( Norcarotenoids)等倍半萜天然产物的全合成[1,2 ] .我们以对映体纯化合物 1为原料 ,实现这类天然产物的不对称全合成 [3～ 6 ] .消旋的化合物 (± ) - 1可以 2 -甲基呋喃和 2 -氯丙烯腈为原料 ,经 3步反应得到 [2 ] .但对映体纯化合物 1的制备尚未见报道 .本文用化学拆分方法 ,成功地制备了对映体纯的 ( + ) - 1和 ( - ) - 1 ,并确定了其绝对构型 .1　结果与讨论为减…     

Effect of substituent in para-substituted anilines on the isomerization rate of 5-vinylbicyclo[2,2,1]hept-2-ene catalyzed by anilinepentacarbonyliron complexes

The isomerization kinetics of 5-vinylbicyclo [2,2,1]-hept-1ene to 5-enthylidenbicyclo [2,2,1] hept-2-ene in the presence of iron pentacarbonyl and parasubstituted anilines has been investigated. The kinetic data correlate with -constants of the substitutes according to Jaffe.

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5- [2,2,1]-2- 5- [2,2,1] -2- - . - .

     

Synthesis and crystal structure of 5-amino-4,6-dicyano-3-dicyanomethylene-1, 8,8-trimethyl-2-azabicyclo[2.2.2]oct-5-ene

5-Amino-4,6-dicyano-3-dicyanomethylene-1,8,8-trimethyl-2-azabicyclo[2.2.2]oct-5-ene has been synthesized. The molecular and crystal structure of this compound has been determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 169–172, January, 1996.     

Synthesis of Cucurbit[5]uril-Spermine-[2]Rotaxanes

Cucurbit[5]uril and decamethylcucurbit[5]uril are cyclic pentamers built from glycoluril or dimethylglycoluril respectively. Two different experimental methods have been used for the synthesis of the different [2]rotaxanes. The formed rotaxanes are characterized using ¹H-NMR spectroscopy, mass spectrometry and elemental analysis. In contrast to cucurbit[5]uril no [2]rotaxane could be obtained with decamethylcucurbit[5]uril.     

Reaction of 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione with hexaethyltriamidophosphite in the presence of diethylammonium chloride. Synthesis and the three-dimensional structure of (1,7,7-trimethyl-2-oxobicyclo[2.2.1]hept-3-yloxy)tris(diethylamino)phosphonium chloride

The reaction of 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione with hexaethyltriamido-phosphite in the presence of diethylammonium chloride afforded a stable quasiphosphonium salt, viz., (1,7,7-trimethyl-2-oxobicyclo[2.2.1]hept-3-yloxy)tris(diethylamino)phosphonium chloride, as one diastereomer (racemate, 1R*,3S*,4S*). Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 383–385, February, 2006.