1,3-Diastereocontrol in acyclic radical allylations

The radical allylation of an acyclic α-hydroxyketone with allyltributyltin under chelation-controlled conditions is reported. Several reaction conditions were explored, including radical initiators, solvents, and temperatures to improve the yield and the diastereomeric ratio. Some Lewis acids, like magnesium bromide etherate and zinc chloride, gave superior diastereomeric ratios (up to 100:1) and good yields.     

Efficient Syntheses of Substituted Carbazoles and Cyclopent[b]indoles from 1-Methyl-3-(benzotriazol-1-ylmethyl)indole

1-Methyl-3-(benzotriazol-1-ylmethyl)indole (1) undergoes lithiation and 1,4-addition with a variety of alpha,beta-unsaturated ketones and aldehydes. Subsequent treatment with an acidic resin in refluxing 1,4-dioxane causes intramolecular cyclization followed by aromatization to furnish a wide range of 1,3-di-, 2,3-di-, and 1,2,3-trisubstituted carbazoles 6a-j and 8 in moderate to excellent yields. NMR study is described to discriminate between structures of types 6 and 8 on the basis of (1)H-(13)C long-range correlation. Treatment of 1 with styrenes in the presence of zinc bromide results in formal [3 + 2] cycloaddition to give cyclopent[b]indoles 14a-c in good yields. When 1 is first lithiated and reacts with electrophiles, the resulting alkylation products undergo similar [3 + 2] additions with styrenes to give 1-functionalized cyclopent[b]indoles 15 and 16with a high degree of stereoselectivity.     

Kobalt(III) ammin-derivate einiger Reineckesalz-Analoga mit Toluidinen

Zusammenfassung Es wurden 39 neue Komplexsalze durch doppelte Umsetzung aus wäßrig-alkohol. Lösungen der folgenden Reineckeat-Analoga: [Cr(NCS)₄(o-Toluidin)₂]^–, [Cr(NCS)₄(m-Toluidin)₂]^– und [Cr(NCS)₄(p-Toluidin)₂]^– und Hexammin-, Monoacido-pentammin-und Diacido-tetrammin-kobalt(III)-komplexsalze erhalten.Es wurden in einigen Fällen Abweichungen in physikochemischen Eigenschaften, wie Farbtönung, Kristallform, Löslichkeit und papierchromatographischeR _F-Werte, bei den stellungsisomeren Salzen vom Typus: Kation·[Cr(NCS)₄(Toluidin)₂] und auch bei den Koordinationsisomerpaaren: [Co(DH)₂(o-Toluidin)₂][Cr(NCS)₄(p-Toluidin)₂] und [Co(DH)₂(p-Toluidin)₂] [Cr(NCS)₄(o-Toluidin)₂], usw. beobachtet.

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Cobalt(III) ammine derivatives of some reineckate analogues with toluidines

39 new complex salts were prepared by double conversion of the reineckate analogues [Cr(SCN)₄(o-toluidine)₂]^–, [Cr(SCN)₄(m-toluidine)₂]^–, and [Cr(SCN)₄(p-toluidine)₂]^– with the hexammine, monoacido-pentammine and diacido-tetrammine complexes of Co(III). In some of the position and coordination isomers deviations from the standard physico-chemical properties, i.e. color, crystal form, solubility and paper chromatographyR _f-values were observed.

     

Alicyclic-Amine-Derived Imine-BF3 Complexes: Easy-to-Make Building Blocks for the Synthesis of Valuable α-Functionalized Azacycles

A new strategy to access α-functionalized alicyclic amines via their corresponding imine-BF₃ complexes is reported. Isolable imine-BF₃ complexes, readily prepared via dehydrohalogenation of N-bromoamines in a base-promoted/18-crown-6 catalyzed process followed by addition of boron trifluoride etherate, undergo reactions with a wide range of organometallic nucleophiles to afford α-functionalized azacycles. Organozinc and organomagnesium nucleophiles add at ambient temperatures, obviating the need for cryogenic conditions. In situ preparation of imine-BF₃ complexes provides access to α-functionalized morpholines and piperazines directly from their parent amines in a single operation. α-Functionalized morpholines can be elaborated further, for instance by installing a second substituent in the α′-position.     

Mono‐ and Binuclear Rhodium and Platinum Complexes of 1, 3, 5‐Trimethyl‐1, 3, 5‐triaza‐2σ3λ3‐phosphorin‐4, 6‐dionyloxy‐substituted Calix[4]arenes

The reaction behaviour of 1, 3, 5‐triaza‐2σ³λ³‐phosphorin‐4, 6‐dionyloxy‐substituted calix[4]arenes towards mono‐ and binuclear rhodium and platinum complexes was investigated. Special attention was directed to structure and dynamic behaviour of the products in solution and in the solid state. Depending on the molar ratio of the reactands, the reaction of the tetrakis(triazaphosphorindionyloxy)‐substituted calix[4]arene ( 4 ) and its tert‐butyl‐derivative ( 1 ) with [(cod)RhCl]₂ yielded the mono‐ and disubstituted binuclear rhodium complexes 2 , 3 , and 5 . In all cases, a C₂‐symmetrical structure was proved in solution, apparently caused by a fast intramolecular exchange process between cone conformation and 1, 3‐alternating conformation. The X‐ray crystal structure determination of 5 confirmed [(calixarene)RhCl]₂‐coordination through two opposite phosphorus atoms with a P ⃜P separation of 345 pm. The complex displays crystallographic inversion symmetry, and the Rh₂Cl₂ core is thus exactly planar. Reaction of 1 and of the bis(triazaphosphorindionyloxy)‐bis(methoxy)‐substituted tert‐butyl‐calix‐[4]arene ( 7 ) with (cod)Rh(acac) in equimolar ratio and subsequent reaction with HBF₄ led to the expected cationic monorhodium complexes 5 and 8 , involving 1, 3‐alternating P‐Rh‐P‐coordination. The cone conformation in solution was proved by NMR spectroscopy and characteristic values of the ¹J(PRh) coupling constants in the ³¹P‐NMR‐spectra. Reaction of equimolar amounts of 4 with (cod)Rh(acac) or (nbd)Rh(acac) led, by substitution of the labile coordinated acetylacetonato and after addition of HBF₄, to the corresponding mononuclear cationic complexes 9 and 10 . Only two of the four phosphorus atoms in 9 and 10 are coordinated to the central metal atom. Displacement of either cycloocta‐1, 5‐diene or norbornadiene was not observed. For both compounds, the cone conformation was proved by NMR spectroscopy. Reaction of 4 with (cod)PtCl₂ led to the PtCl₂‐complex ( 11 ). As for all compounds mentioned above, only two phosphorus atoms of the ligand coordinate to platinum, while two phosphorus atoms remain uncoordinated (proved by δ³¹P and characteristic values of ¹J(PPt)). NMR‐spectroscopic evidence was found for the existence of the cone conformation in the cis‐configuration of 11 .     

Calix[4]arene‐based Bis‐phosphonites,Bis‐phosphites,and Bis‐O‐acyl‐phosphites as Ligands in the Rhodium(I)‐catalyzed Hydroformylation of 1‐Octene

New calix[4]arene‐based bis‐phosphonites, bis‐phosphites and bis‐O‐acylphosphites were synthesized and characterized. Treatment of these P‐ligands with selected rhodium and platinum precursors led to mononuclear complexes that were satisfactorily characterized. The solid state structure of the dirhodium(I) complex 14 has been determined by X‐ray diffraction. The two rhodium centres are bridged by two chloro ligands; one rhodium atom is further coordinated by calix[4]arene phosphorus atoms and the other by cyclooctadiene. The new calix[4]arene P‐ligands were tested in the Rh(I) catalyzed hydroformylation of 1‐octene. All Rh(I) complexes catalyzed the reaction leading to high chemoselectivity with regard to the formation of aldehydes. Yields and n/iso‐selectivities depended on the reaction conditions. Average yields of 80 % and n/iso‐ratios of about 1.3 to 1.5 were observed. High yields of aldehydes can be achieved using the methoxy substituted P‐ligands at low Rh:ligand ratios.     

LB膜中混合聚集体的光致荧光特性研究

研究了不同活性分子（半花菁和氐盐）混合聚集体的形成以及紫外光照射对ＬＢ交替多层膜光致荧光（ＰＬ）特性的影响。在半花菁和氐盐混合的ＬＢ膜中,由于不同分子间较强的相互作用使混合膜的荧光光谱较纯半花菁和氐盐分子膜分别发生了蓝移和红移。利用紫外光照射可以使分子的聚集体部分分解甚至破坏分子的结构,导致光致荧光强度明显减弱。     

Direct electrochemistry of bovine heart cytochrome c facilitated by cysteine derivatives and analogues. Some effects of facilitator structure

Bovine heart cytochrome c electrochemistry was investigated by cyclic voltammetry using gold electrodes modified by self-assembled monolayers of cysteine and some of its derivatives, including glutathione. Glutathione shows a peculiar dependence of the facilitating ability on the oxidation state of the sulfur functionality. Whereas the disulfide form acts as an efficient facilitator, the thiol form is completely inactive. This behavior was accounted for by the lower stability of adsorbed thiol layers as compared to disulfide layers. Apparently, small molecules of cysteine derivative form rather stable adsorbed layers with a high degree of dimer formation. Conversely, reduced glutathione is not able to turn into the disulfide form in the adsorbed layer. Consequently, only the layer produced by the adsorption of the disulfide form itself is stable enough for promoting direct electron transfer reactions of cyt c. Electronic Publication     

Darstellung und Sulfurierung von 4,5-Benzo-2-{[2-(dimethylamino)ethyl]methyl-amino}-3-methyl-1,3,2-oxazaphosphorinan-6-on; Molekülstruktur eines Tetracarbonylmolybdän(0)-Chelatkomplexes

4,5-Benzo-2-{[2-(dimethylamino)ethyl]methylamino}-3-methyl-1,3,2-oxazaphosphorinan-6-one – Preparation, Sulfuration, and Molecular Structure of a Tetracarbonyl Molybdenum Derivative The synthesis of the title compound 4 is described. It reacts with sulfur to yield the thiophosphoryl derivative 5 . The structure of the molybdenum(0) complex 6 , containing 4 as a bidentate ligand, was established by X-ray analysis and is compared to that of the related 2-{[2-(dimethylamino)ethyl]methyl-amino}-1,3,2-benzodioxaphosphole-tetracarbonylchromium(0)-complex 7 [1]. 6 , similarly to 7 , shows a nearly rectangular ?bite”? angle, with 4 functioning as a chelating ligand, coordinating to Mo(0) via P(III) and the nitrogen atom of the NMe₂ group. The heterocyclic part of the ligand displays a distorted envelope configuration.     

Temperature field modeling during multi-modes CO2 laser irradiation of human enamel

We examine the temperature fields of human enamel [Yu D, Fox JL, Hsu J, Lynn Powell G, Higuchi WI. Computer simulation of surface temperature profiles during CO₂ laser irradiation of human enamel. Opt Eng 1993; 32(2)] during multi-modes CO₂ laser irradiation. For this we use the integral transform method as well as direct and inverse Laplace transform [Oane M, Sporea D. Temperature profiles modeling in IR optical components during high power laser irradiation. Infrared Phys Technol 2001; 42(1): 31–40; Oane M, Sporea D. Study of heat transfer in IR optical components during CO₂ laser irradiation. Proc SPIE 2001; 4430: 898–904; Oane M. Mathematical modeling of the thermal field distributions in solids under multiple laser irradiations. Proc SPIE 2003; 5227: 329–34; Oane M, Apostol I, Timcu A. Temperature field modeling in laser heated metals for laser cleaning of surfaces. Proc SPIE 2003; 5227: 323–8]. The enamel block is modeled as homogeneous cylinder in three dimensions. Results indicate that (i) the thermal field depends on multi-modes structure; (ii) heat transfer coefficient plays an important role in temperature distribution.