Organosulfur compounds: electrophilic reagents in transition-metal-catalyzed carbon-carbon bond-forming reactions

Transition-metal-catalyzed carbon-carbon bond-forming reactions are among the most powerful methods in organic synthesis and play a crucial role in modern materials science and medicinal chemistry. Recent developments in the area of ligands and additives permit the cross-coupling of a large variety of reactants, including inexpensive and readily available sulfonyl chlorides. Their desulfitative carbon-carbon cross-coupling reactions (Negishi, Stille, carbonylative Stille, Suzuki-Miyaura, and Sonogashira-Hagihara-type cross-couplings and Mizoroki-Heck-type arylations) are reviewed together with carbon-carbon cross-coupling reactions with other organosulfur compounds as electrophilic reagents.     

Cross-linking of polyolefins: a study by thermoporosimetry with benzene derivatives as swelling solvents.

The solvents o-, m-, p-xylene, p-dichlorobenzene, 1,2,4-trichlorobenzene, and naphthalene were calibrated as condensates used in the thermoporosimetry technique. Exponential relationships were found connecting the pore radii R(p) (in nm) and the freezing-point depression of the swelling solvent deltaT (in degrees C) on the one hand and the apparent energy of crystallization W(a) (in J cm(-3)) and deltaT on the other hand: R(p) = t exp[-1/(c deltaT)]; W(a) = W0 exp(deltaT/f). Pore- or mesh-size distributions can be derived from differential scanning calorimetry results by using the following equation: dV(p)/dR(p) = k{[cY(T)deltaT2]/[W(a)R(p)]}. All the numerical parameters were determined. Polyethylene and polypropylene samples, cross-linked with high-energy electrons or gamma-rays, were submitted to thermoporosimetry study. Relative mesh-size distributions, which depend on the polymer/solvent pair, were calculated for these polyolefins with o-, m-, and p-xylene as solvent and were found to be in the same sequence as those of their degrees of swelling and the irradiation doses received.     

Diaminocarbene- and Fischer-carbene complexes of palladium and nickel by oxidative insertion: preparation, structure, and catalytic activity

Oxidative insertion of [Pd(PPh3)4] or [Ni(cod)2]/PPh3 into the C-Cl bond of various 2-chloroimidazolinium- and other -amidinium salts affords metal-diaminocarbene complexes in good to excellent yields. This procedure is complementary to existing methodology in which the central metal does not change its oxidation state, and therefore allows to incorporate carbene fragments that are difficult to access otherwise. The preparation of a variety of achiral as well as enantiomerically pure, chiral metal-NHC complexes (NHC = N-heterocyclic carbene) and metal complexes with acyclic diaminocarbene ligands illustrates this aspect. Furthermore it is shown that oxidative insertion also paves a way to prototype Fischer carbenes of Pd(II). Since the required starting materials are readily available from urea- or thiourea derivatives, this novel approach allows for substantial structural variations of the ligand backbone. The catalytic performance of the resulting library of nickel- and palladium-carbene complexes has been evaluated by applications to prototype Suzuki-, Heck-, and Kumada-Corriu cross-coupling reactions as well as Buchwald-Hartwig aminations. It was found that even Fischer carbenes show appreciable catalytic activity. Moreover, representative examples of all types of neutral and cationic metal-carbene complexes formed in this study have been characterized by X-ray crystallography.     

Six‐ and Eightfold Palladium‐Catalyzed Cross‐Coupling Reactions of Hexa‐ and Octabromoarenes

Palladium‐catalyzed sixfold coupling of hexabromobenzene ( 20 ) with a variety of alkenylboronates and alkenylstannanes provided hexaalkenylbenzenes 1 in up to 73 % and 16 to 41 % yields, respectively. In some cases pentaalkenylbenzenes 21 were isolated as the main products (up to 75 %). Some functionally substituted hexaalkenylbenzene derivatives containing oxygen or sulfur atoms in each of their six arms have also been prepared (16 to 24 % yield). The sixfold coupling of the less sterically encumbered 2,3,6,7,10,11‐hexabromotriphenylene ( 24 ) gave the desired hexakis(3,3‐dimethyl‐1‐butenyl)triphenylene ( 25 ) in 93 % yield. The first successful cross‐coupling reaction of octabromonaphthalene ( 26 ) gave octakis‐(3,3‐dimethyl‐1‐butenyl)naphthalene ( 27 ) in 21 % yield. Crystal structure analyses disclose that, depending on the nature of the substituents, the six arms are positioned either all on the same side of the central benzene ring as in 1 a and 1 i , making them nicely cup‐shaped molecules, or alternatingly above and below the central plane as in 1 h and 23 . In 27 , the four arms at C‐1,4,6,7 are down, while the others are up, or vice versa. Upon catalytic hydrogenation, 1 a yielded 89 % of hexakis(tert‐butylethyl)benzene ( 23 ). Some efficient accesses to alkynes with sterically demanding substituents are also described. Elimination of phosphoric acid from the enol phosphate derived from the corresponding methyl ketones gave 1‐ethynyladamantane ( 3 b , 62 % yield), 1‐ethynyl‐1‐methylcyclohexane ( 3 c , 85 %) and 3,3‐dimethylpentyne ( 3 e , 65 %). 1‐(Trimethylsilyl)ethynylcyclopropane ( 7 ) was used to prepare 1‐ethynyl‐1‐methylcyclopropane ( 3 d ) (two steps, 64 % overall yield). The functionally substituted alkynes 3 f – h were synthesized in multistep sequences starting from the propargyl chloride 11 , which was prepared in high yields from the dimethylpropargyl alcohol 10 (94 %). The alkenylstannanes 19 were prepared by hydrostannation of the corresponding alkynes in moderate to high yields (42–97 %), and the alkenylboronates 2 and 4 by hydroboration with catecholborane (27–96 % yield) or pinacolborane (26–69 % yield).     

Comparative methods in the determination of wax content and pour points of crude oils

In this research, differential scanning calorimetry (DSC) and gas chromatography is used to determine the wax content of fourteen crude oils of different sources. Different empirical equations were applied to compare the wax content of crude oils. For the fourteen crude oil samples with the wax content ranging from 7.5 to 43.8 mass%, it was observed that the results of empirical equations were in good agreement with those determined by DSC and GC. Accordingly, a correlation between ASTM pour point and the temperature at which 2 mass% of wax has precipitated out from crude oil is developed.     

Metastable systems driven by colored noise: The stationary state

The influence of the Bardeen-Herring back-jump correlations on the Fermi-Dirac statistics of the one-dimensional nonhomogeneous fermionic lattice gas is studied by the Monte Carlo simulation technique and semianalytically. The resulting distribution is obtained, exhibiting increased population of the lower levels in comparison to the Fermi-Dirac statistics.     

Bistatic scattering by arbitrarily shaped objects with rough surface at optical and infrared frequencies

The scattering cross sections for arbitrarily shaped dielectric objects with rough surface are determined for optical and infrared frequencies using the Kirchhoff approximation. The formula of the coherent scattering cross section is derived, and numerical method of incoherent scattering cross section is given. As a specific example, the infrared laser scattering cross sections of rough spheres are calculated at 1.06 m.     

Decay of correlations in surface models

A convergent low-temperature expansion for a variety of models of twodimensional surfaces is presented. It yields existence of the thermodynamic limit for the pressure and correlation functions as well as analyticity inz =e ^– In addition, the estimates give exponential decay of truncated correlations, which proves the existence of a gap in the spectrum of the transfer matrix below the ground state eigenvalue. Two particular examples included in the general framework are the solid-on-solid and discrete Gaussian models.Supported in part by the National Science Foundation under grant No. PHY 79-16812.     

Facile Synthesis and Palladium‐Catalyzed Cross‐Coupling Reactions of 2,3‐Bis(pinacolatoboryl)‐1,3‐butadiene

Treatment of 1,1‐bis(pinacolatoboryl)ethene with an excess of 1‐bromo‐1‐lithioethene gave 2,3‐bis(pinacolatoboryl)‐1,3‐butadiene in high yield. Palladium‐catalyzed cross‐coupling of the resulting diborylbutadiene with aryl iodides took place smoothly in the presence of a catalytic amount of Pd(OAc)₂/PPh₃ and aqueous KOH to give 2,3‐diaryl‐1,3‐butadienes in good yields. The coupling reaction with commercially available 4‐acetoxyphenylmethyl chloride under the same conditions followed by hydrolysis of the acetyl groups gave anolignan B in a one‐pot manner. A variety of [3]‐ to [6]dendralenes were synthesized by palladium‐catalyzed coupling of the diene or 1,1‐bis(pinacolato)borylethene with alkenyl or dienyl halides, respectively, in good yields.     

Back-and-forth shooting method for solving two-point boundary-value problems

The paper proposes a special iterative method for a nonlinear TPBVP of the form (t)=f(t, x(t),p(t)), (t)=g(t, x(t),p(t)), subject toh(x(0),p(0))=0,e(x(T),p(T))=0. Certain stability properties of the above differential equations are taken into consideration in the method, so that the integration directions associated with these equations respectively are opposite to each other, in contrast with the conventional shooting methods. Via an embedding and a Riccati-type transformation, the TPBVP is reduced to consecutive initial-value problems of ordinary differential equations. A preliminary numerical test is given by a simple example originating in an optimal control problem.