（E）－β，γ－UNSATURATED NITRILES FROM DIMETHYLSULFONIUM CYANOMETHYLIDE AND 9－ALKENYL－9－BORABICYCLO［3，3，1］NONANES

（Ｅ）－β，γ－ＵＮＳＡＴＵＲＡＴＥＤＮＩＴＲＩＬＥＳＦＲＯＭＤＩＭＥＴＨＹＬＳＵＬＦＯＮＩＵＭＣＹＡＮＯＭＥＴＨＹＬＩＤＥＡＮＤ９－ＡＬＫＥＮＹＬ－９－ＢＯＲＡＢＩＣＹＣＬＯ［３，３，１］ＮＯＮＡＮＥＳＮａｎＳｈｅｎｇＬＩ；ＭｉｎＺｈｉＤＥＮＧ；Ｙ...     

HYDROLYTIC CLEAVAGE OF ACMET-GLY PROMOTED BY CIS-[Pd(MET)(D_2O)_2](NO_3)_2

ＨＹＤＲＯＬＹＴＩＣＣＬＥＡＶＡＧＥＯＦＡＣＭＥＴ－ＧＬＹＰＲＯＭＯＴＥＤＢＹＣＩＳ－［Ｐｄ（ＭＥＴ）（Ｄ２Ｏ）２］（ＮＯ３）２￥ＸｉａｏＨｕａＣＨＥＮ；ＬｏｎｇＧｅｎＺＨＵ；Ｎ．Ｍ．Ｋｏｓｔｉｃ（ＣｏｏｒｄｉｎａｔｉｏｎＣｈｅｍｉｓｔｒｙＩｎｓｔｉ...     

AlCl_3／SbCl_3引发α－蒎烯阳离子聚合反应──引发活性种本质研究

考察了复合催化剂ＡｌＣｌ_３／ＳｂＣｌ_３的不同配制方法和质子捕捉剂２，６－二异丁基－４－甲基吡啶（ＤＴＢＭＰ）对α－蒎烯阳离子聚合反应的影响。结果表明，ＡｌＣｌ_３和ＳｂＣｌ_３加热熔融复合比简单复合的引发聚合活性更高；ＤＴＢＭＰ对该复合催化剂的聚合反应速率及其产物分子量分布均无明显影响，证明该复合催化剂形成的活性种本质上与质子Ｈ活性种不同，是新型活性种。根据２７ＡｌＮＭＲ对该体系活性种分析结果，认为引发阳离子是［Ｓｂ（Ｖ）Ｃｌ_４］，抗衡阴离子是［Ａｌ_２Ｃｌ_７］     

手性助剂诱导下的α,β-不饱和酮的不对称加氢反应及其在合成(R)-麝香酮中的应用

在ＴＨＦ溶液中，４０－６０℃及０．３－０．５ＭＰａ氢压条件下，［ＲｕＣｌ２（ｃｈｔ）］２＋（Ｓ）－ＢＩＮＡＰ手性催化剂体系催化不饱和手性缩酮２选择加氢，再经脱去手性二醇，即可高立体选择性地制得（Ｒ）－３－甲基环十五烷酮（４，（Ｒ）－（－）－麝香酮），化学收率≥９５％，光学纯度≥９７％．手性缩酮２由Ｄ－苏糖醇或Ｄ－葡萄糖衍生的手性二醇３与３－甲基环十五烯－２－酮１生成．     

ASYMMETRIC SYNTHESIS ⅩⅩⅧ: ENANTIOSELECTIVE REDUCTION OF AROMATIC KETONES CATALYZED BY NEW CHIRAL CATALYST-(4R,8R,9S)-CAMPHANE[8,9-b]-1,3,2-OXATHIOBOROLIDINE

ＡＳＹＭＭＥＴＲＩＣＳＹＮＴＨＥＳＩＳⅩⅩⅧ：ＥＮＡＮＴＩＯＳＥＬＥＣＴＩＶＥＲＥＤＵＣＴＩＯＮＯＦＡＲＯＭＡＴＩＣＫＥＴＯＮＥＳＣＡＴＡＬＹＺＥＤＢＹＮＥＷＣＨＩＲＡＬＣＡＴＡＬＹＳＴ－（４Ｒ，８Ｒ，９Ｓ）－ＣＡＭＰＨＡＮＥ［８，９－ｂ］－１，３，...     

SYNTHESIS OF 1H，1＇H BIS（BENZ－△~4－IMIDAZOLINE）2，2＇－SPIRO－TITANIUM DICHLORIDE

ＳＹＮＴＨＥＳＩＳＯＦ１Ｈ，１＇ＨＢＩＳ（ＢＥＮＺ－△~４－ＩＭＩＤＡＺＯＬＩＮＥ）２，２＇－ＳＰＩＲＯ－ＴＩＴＡＮＩＵＭＤＩＣＨＬＯＲＩＤＥＷｅｉＲｏｎｇｂａｏ；ＬｉａｎｇＹａ；ＷｕＪｉｎｇｕｏ；ＸｕｅＱｉｆｅｎｇ（Ｄｅｐｔ．ｏｆＣｈｅｍ．Ｅｎｇ．...     

STRUCTURAL MODIFICATION OF 11－ISOPROPYLIDENE endo－TRICYCLO［6．2．1．0~（2，7）］UNDECA－4， 9－DIENE－3，6－DIONE TO IMPROVE THE STABILITY

ＳＴＲＵＣＴＵＲＡＬＭＯＤＩＦＩＣＡＴＩＯＮＯＦ１１－ＩＳＯＰＲＯＰＹＬＩＤＥＮＥｅｎｄｏ－ＴＲＩＣＹＣＬＯ［６．２．１．０￣（２，７）］ＵＮＤＥＣＡ－４，９－ＤＩＥＮＥ－３，６－ＤＩＯＮＥＴＯＩＭＰＲＯＶＥＴＨＥＳＴＡＢＩＬＩＴＹ￥ＸｉａｏＰｅｉＧ...     

CONVERSION OF KETONES INTO1，1－DISUBSTITUTED－2，3，3－TRIFLUORO－2－PROPEN －1－OLSWITH1，1－DIBROMO－1，2，2，2－TETRLUORO ETHANE／MAGNESIUM REAGENT

ＣＯＮＶＥＲＳＩＯＮ　ＯＦ　ＫＥＴＯＮＥＳ　ＩＮＴＯ１，１－ＤＩＳＵＢＳＴＩＴＵＴＥＤ－２，３，３－ＴＲＩＦＬＵＯＲＯ－２－ＰＲＯＰＥＮ　－１－ＯＬＳＷＩＴＨ１，１－ＤＩＢＲＯＭＯ－１，２，２，２－ＴＥＴＲＬＵＯＲＯ　ＥＴＨＡＮＥ／ＭＡＧＮＥＳＩＵＭ...     

1-酰氧(胺)-2,8,9-三氧杂-5-氮杂-1-锡杂三环[3.3.3.01.5]十一烷的合成和结构研究

合成了１４个新化合物：１－酰氧（胺）基－２，８，９－三氧杂－５－氮杂－１－锡杂三环［３．３．３．０１．５］十一烷．由ＩＲ、１ＨＮＭＲ、１３ＣＮＭＲ和１１９ＳｎＮＭＲ及元素分析确定其结构．该类化合物在ＣＤＣｌ３中可能形成六配位化合物，而在ＤＭＳＯ中，溶剂分子参与Ｓｎ原子配位，聚合体解聚为六配位化合物．     

PARAMAGNETIC AND DIAMAGNETIC DICOPPER（Ⅱ） COMPLEXES WITH DI－SCHIFF BASE DERIVED FROM 2－HYDROXY－1－NAPHTHALDEHYDE AND1，3－DIANINO－2－PROPANOL

ＰＡＲＡＭＡＧＮＥＴＩＣＡＮＤＤＩＡＭＡＧＮＥＴＩＣＤＩＣＯＰＰＥＲ（Ⅱ）ＣＯＭＰＬＥＸＥＳＷＩＴＨＤＩ－ＳＣＨＩＦＦＢＡＳＥＤＥＲＩＶＥＤＦＲＯＭ２－ＨＹＤＲＯＸＹ－１－ＮＡＰＨＴＨＡＬＤＥＨＹＤＥＡＮＤ１，３－ＤＩＡＮＩＮＯ－２－ＰＲＯＰＡＮＯＬ...     

A convenient new route to piperidines, pyrrolizidines, indolizidines, and quinolizidines by cyclization of acetylenic sulfones with beta and gamma-chloroamines. Enantioselective total synthesis of indolizidines (-)-167B, (-)-209D, (-)-209B, and (-)-207A

The methyl esters of (L)-phenylalanine and (L)-methionine underwent conjugate additions via their free amino groups to 1-(p-toluenesulfonyl)hexyne, followed by intramolecular acylation of the corresponding enamide anions and tautomerization to afford 2-benzyl-5-n-butyl-3-hydroxy-4-(p-toluenesulfonyl)pyrrole and 5-n-butyl-3-hydroxy-2-(2-methylthioethyl)-4-(p-toluenesulfonyl)pyr role, respectively. The conjugate additions of a series of acyclic and cyclic secondary beta- and gamma-chloroamines to acetylenic sulfones proceeded similarly under mild conditions. The resulting adducts were deprotonated with LDA in THF at -78 degrees C, and the resulting sulfone-stabilized carbanions underwent intramolecular alkylation to afford cyclic enamine sulfones. Thus, acyclic gamma-chloroalkyl-benzylamines afforded the corresponding 2- or 2,6-disubstituted piperidines, while 2-(chloromethyl)pyrrolidines, 2-(2-chloroethyl)pyrrolidines, 2-(chloromethyl)piperidines, and 2-(2-chloroethyl)piperidines produced the corresponding 3-substituted pyrrolizidines, 5- or 3-substituted indolizidines, and 4-substituted quinolizidines, respectively. 8-Methyl-5-substituted indolizidines were also prepared from the appropriate methyl-substituted chloroamine precursor. Enantioselective syntheses were achieved by employing chiral chloroamines derived from amino acids or other enantiopure precursors. Further transformations of several of the products provided concise syntheses of four dendrobatid alkaloids. Thus, reduction of (8aS)-5-n-propyl-6-(p-toluenesulfonyl)-delta5,6-indolizidine with sodium cyanoborohydride in trifluoroacetic acid, followed by reductive desulfonylation, afforded (-)-indolizidine 167B. The corresponding 5-n-hexyl derivative similarly produced (-)-indolizidine 209D, while (-)-(8R, 8aS)-8-methyl-5-n-pentyl-6-(p-toluenesulfonyl)-delta5,6-indo lizidine furnished (-)-indolizidine 209B. Finally, the similar reduction and debenzylation of (-)-(8R,8aS)-5-(2-benzyloxyethyl)-8-methyl-6-(p-toluenesulfo nyl)-delta5,6-indolizidine produced the corresponding 5-hydroxyethyl indolizidine. This was subjected to chlorination of the alcohol group with thionyl chloride and substitution with a higher order allyl cuprate reagent to afford (-)-indolizidine 207A.     

Aromaticity and antiaromaticity in 4-, 6-, 8-, and 10-membered conjugated hydrocarbon rings

Recently, we presented a molecular orbital (MO) model of aromaticity that explains, in terms of simple orbital-overlap arguments, why benzene (C(6)H(6)) has a regular structure with delocalized double bonds whereas the geometry of 1,3-cyclobutadiene (C(4)H(4)) is distorted with localized double bonds. Here, we show that the same model and the same type of orbital-overlap arguments also account for the irregular and regular structures of 1,3,5,7-cyclooctatetraene (C(8)H(8)) and 1,3,5,7,9-cyclodecapentaene (C(10)H(10)), respectively. Our MO model is based on accurate Kohn-Sham DFT analyses of the bonding in C(4)H(4), C(6)H(6), C(8)H(8), and C(10)H(10) and how the bonding mechanism is affected if these molecules undergo geometrical deformations between regular, delocalized ring structures and distorted ones with localized double bonds. The propensity of the pi electrons is always to localize the double bonds, against the delocalizing force of the sigma electrons. Importantly, we show that the pi electrons nevertheless determine the localization (in C(4)H(4) and C(8)H(8)) or delocalization (in C(6)H(6) and C(10)H(10)) of the double bonds.     

Synthesis of lithium,sodium, cesium,and calcium salts of (E)-4- or (E,S)-3-methyl-2-(5-arylisoxazol-3-yl)-methyleneaminobutanoic, (E,S)-4-methyl-2- or (E,2S,3S)-3-methyl-2-(5-arylisoxazol-3-yl)methyleneaminopentanoic,and (E)-6-(5-arylisoxazol-3-yl)methyleneaminohexanoic acids

Preparative method for the synthesis of lithium, sodium, cesium, and calcium salts of (E)-4-(5-arylisoxazol-3-yl)methyleneaminobutanoic, (E)-6-(5-arylisoxazol-3-yl)methyleneaminohexanoic, (E,S)-3-methyl-2-(5-arylisoxazol-3-yl)methyleneaminobutanoic, (E,S)-4-methyl-2-(5-arylisoxazol-3-yl)methyleneaminopentanoic and (E,2S,3S)-3-methyl-2-(5-arylisoxazol-3-yl)methyleneaminopentanoic acids was developed by reacting 5-phenyl(4-tolyl)isoxazole-3-carbaldehydes with amino acids like 4-aminobutyric and 6-aminocaproic acids, L-valine, L-leucine or L-isoleucine in the presence of lithium hydride, sodium methoxide, cesium carbonate or calcium hydride in boiling methanol.     

Photolytic, thermal, addition, and cycloaddition reactions of 2-diazo-5,6- and -3,8-disubstituted acenaphthenones

Preparation and varied thermal and photolytic reactions of 2-diazo-5,6-(disubstituted)acenaphthenones (11a-d) and 2-diazo-3,8-dimethoxyacenaphthenone (12) are reported. Alcohols react thermally and photolytically with 11a-c with losses of N(2) to yield 2-alkoxynaphthenones (24a,band 47a,b) and acenaphthenones (25 and 48a,b). Aniline and diphenylamine are converted by 11a-c at 180 degrees C to acenaph[1,2-b]indoles (29a,b and 53a,b). Thermolyses of 11a-c at approximately 450 degrees C (0.15 mmHg) yield reduction products 25 and 48a,b, respectively. Wolff rearrangements to 1,8-naphthyleneketenes (15a-d) and/or their derivatives are not observed in the above experiments. Oxygen converts 11a-c thermally to acenaphthenequinones (19a-c) and/or 1,8-naphthalic anhydrides. Insertion, addition, substitution, and/or isomerization reactions occur upon irradiation of 2-diazoacenaphthenones in cyclohexane, benzene, and tetrahydrofuran. Photolysis of 11d in benzene in the presence of O(2) yields the insertion-oxidation product 2-hydroxy-5,6-dinitro-2-phenylacenaphthenone (60). Photolyses of 11a-c in nitriles result in N(2) evolution and dipolar cycloaddition to give acenaph[1,2-d]oxazoles (41 and 61a,b). Acetylenes undergo thermal and photolytic cycloaddition/1,5-sigmatropic rearrangement reactions with 11a-d with N(2) retention to give pyrazolo[5,1-a]quinolin-7-ones (69f-j). 2-Diazoacenaphthenones 1a and 11a react thermally and photolytically with electronegatively-substituted olefins with N(2) expulsion to yield (E)- and (Z)-2-oxospiro[acenaphthylene-1(2H),1'cyclopropanes] 73a-c and 74a-c, respectively. The mechanisms of the reactions of 1a, 11a-d, and 12 reported are discussed.     

Regioisomerism in the Ritter reaction. 1. Synthesis of 3,3,5,6,7-, 3,3,6,7,8-, 3,3,5,7,8-, and 3,3,5,6,8-pentamethyl-3,4-dihydroisoquinolines from 1,2,3- and 1,2,4-trimethylbenzenes

Reactions of 1,2,3- or 1,2,4-trimethylbenzene with isobutyraldehyde and ethyl cyanoacetate (ECA) or reactions of the corresponding 1-aryl-2-methylpropan-1-ols with ECA afforded isomeric 3,3,5,6,7-, 3,3,6,7,8-, 3,3,5,7,8-, and 3,3,5,6,8-pentamethyl-3,4-dihydroisoquinolines. Isomerization is explained as the ring opening of a spiran intermediate in two possible ways followed by the Jacobsen rearrangement.     

Free-radical-mediated conjugate additions. Enantioselective synthesis of butyrolactone natural products: (-)-enterolactone, (-)-arctigenin, (-)-isoarctigenin, (-)-nephrosteranic acid, and (-)-roccellaric acid

Lewis acid-mediated conjugate addition of alkyl radicals to a differentially protected fumarate 10 produced the monoalkylated succinates with high chemical efficiency and excellent stereoselectivity. A subsequent alkylation or an aldol reaction furnished the disubstituted succinates with syn configuration. The chiral auxiliary, 4-diphenylmethyl-2-oxazolidinone, controlled the stereoselectivity in both steps. Manipulation of the disubstituted succinates obtained by alkylation furnished the natural products (-)-enterolactone, (-)-arctigenin, and (-)-isoarctigenin. The overall yields for the target natural products were 20-26% over six steps. Selective functionalization of the disubstituted succinates obtained by aldol condensation gave the paraconic acid natural products (-)-nephrosteranic acid (8) and (-)-roccellaric acid (9). The overall yield of the natural products 8 and 9 over four steps was 53% and 42%, respectively.     

Structures and related properties of AgX bearing 3,3'-thiobispyridine (X- = NO3-, BF4-, CLO4-, and PF6-

Infinite molecular helices [Ag(3,3'-Py2S)]X (3,3'-Py2S = 3,3'-thiobispyridine; X- = BF4-, ClO4-, and PF6-) have been rationally constructed or induced. Crystallographic characterization (X- = BF-, monoclinic P2(1)/n, a = 8.946(3) A, b = 14.130(2) A, c = 10.124(2) A, beta = 107.83(2) degrees, V = 1218.3(5) A3, Z = 4, R = 0.0351; X- = ClO4-, monoclinic P2(1)/n, a = 8.884(1) A, b = 14.305(3) A, c = 10.110(1) A, beta = 106.78(1) degrees, V = 1230.1(3) A3, Z = 4, R = 0.0417; X- = PF6-, monoclinic P2(1)/c, a = 10.959(2) A, b = 9.808(2) A, c = 14.065(3) A, beta = 112.03(2) degrees, V = 1401.4(5) A3, Z = 4, R = 0.0442) reveals that the skeletal structure is an oblong cylindrical cationic helix consisting of alternating Ag(I) and 3,3'-Py2S species and that its counteranions are pinched in two columns inside each helix. The formation of the helical coordination polymer appears to be primarily associated with a suitable combination of the skewed conformer of 3,3'-Py2S and the potential linear geometry of the N-Ag(I)-N bond. However, the framework of the nitrate analogue [Ag(3,3'-Py2S)NO3] (monoclinic P2(1)/c, a = 8.177(2) A, b = 10.291(1) A, c = 14.771(2) A, beta = 102.19(1) degrees, V = 1214.9(4) A3, Z = 4, R = 0.0300) is a two-dimensional network consisting of an 18-membered ring unit, where each 3,3'-Py2S acts as a N,N',S- tridentate ligand connecting three tetrahedral silver(I) ions with the monodentate nitrate weakly bonded to the silver (Ag.O = 2.65(1) A) rather than acting as a counteranion. The anion exchange of [Ag(3,3'-Py2S)NO3] with BF4-, ClO4-, or PF6- has been accomplished in aqueous media. The two-dimensional networks are easily converted into the helices via the anion exchange, but the reverse anion exchange proceeds slightly. Thermal analyses indicate a relationship between the thermal stabilities and the structural properties.     

Deformed phthalocyanines: synthesis and characterization of zinc phthalocyanines bearing phenyl substituents at the 1-, 4-, 8-, 11-, 15-, 18-, 22-, and/or 25-positions

The synthesis of a series of zinc phthalocyanines partially phenyl-substituted at the 1-, 4-, 8-, 11-, 15-, 18-, 22-, and/or 25-positions (the so-called alpha-positions) is reported. Macrocycle formation based on 3,6-diphenylphthalonitrile, o-phthalonitrile, and zinc acetate predominantly yielded the near-planar disubstituted complex and opposite tetrasubstituted isomer, while the lithium method yielded the sterically hindered hexasubstituted complex and adjacent tetrasubstituted isomer. All compounds have been characterized by 1H NMR, MALDI-TOF-MS, and elemental analysis methods. In addition, crystal structures have been solved for the di-, hexa-, and octasubstituted complexes and the adjacent tetrasubstituted isomer. DFT geometry optimization calculations predict more highly deformed structures than those observed in the crystals. The packing force of the crystals cannot therefore be ignored, particularly for the less phenyl-substituted derivatives. The crystal structures have revealed that overlap of the phenyl groups causes substantial deformation of the phthalocyanine (Pc) ligands within the crystals, while strong pi-pi stacking in the remainder of the Pc moiety lacking phenyl substituents can suppress the impact of the deformation. Absorption spectra show sizable red shifts of the Q-band with increasing number of phenyl groups. Analysis of the results of absorption spectra and electrochemical measurements reveals that a substantial portion of the red shift is attributable to the ring deformations. Molecular orbital calculations lend further support to this conclusion. A moderately intense absorption band emerging at around 430 nm for highly deformed octaphenyl-substituted zinc Pc can be assigned to the HOMO-->LUMO+3 transition, which is parity-forbidden for planar Pcs, but becomes allowed since the ring deformations remove the center of symmetry.     

Synthesis and cyclizations of N-(2,3-, 3,4- and 3,5-dimethylphenyl)-beta-alanines

A series of 1-aryl substituted dihydro-, 5-methyl-dihydro- and 6-methyl-dihydro-2,4(1H,3H)pyrimidinediones and their 2-thio analogues were obtained by reaction of the corresponding beta-alanines or alpha-methyl- and beta-methyl-beta-alanines with urea or potassium thiocyanate. The reaction of N-(2,3- and 3,5-dimethylphenyl)-alpha-methyl-beta-alanines with ethyl acetoacetate gave 1-(2,3- or 3,5-dimethylphenyl)-2,5-dimethyl-1,4,5,6-tetrahydro-4(1H)pyridones. The combined spectral data obtained by (1)H-, (13)C-,(1)H/(13)C (HETCOR) NMR and IR provided useful information about the structure of the products synthesized in this work.     

Cosorption of Zn(II) and 2-, 3-, or 4-aminopyridine by montmorillonite

Data from acid-base titrations at 25 degrees C of Zn(NO(3))(2) and 2-, 3-, or 4-aminopyridine in 10 mM KNO(3) as background electrolyte suggested that soluble complexes ZnL(2+) and Zn(OH)L(+) form, where L represents aminopyridine. Zinc-hydroxyaminopyridine complexes have not been reported previously. The cosorption of Zn(II) with each of the aminopyridines to K-saturated Wyoming (SWy-K) and Texas (STx-K), and Ca-enriched Texas (STx-Ca) montmorillonites was measured at 25 degrees C, with 10 mM KNO(3) or 3.3 mM Ca(NO(3))(2) as background electrolyte. Comparison with previous data for sorption of Zn(II) and the aminopyridines separately and surface complexation modeling of the cosorption data showed that under acid conditions competition between Zn(2+) and aminopyridinium ions for the permanent negatively charged sites of montmorillonite results in suppression of the uptake of each sorbate by the other, but only when a large excess of the competing sorbate is present. Under alkaline conditions the sorption of Zn(II) was not affected by the presence of even a large excess of aminopyridine, but the sorption of 4-aminopyridine in particular was slightly enhanced when a large excess of Zn(II) was present. The enhancement was attributed to the formation of metal-bridged ternary surface complexes at the variable-charge sites on the edges of the montmorillonite crystals.