Regioselective hydrophenylation of olefins catalyzed by an Ir(III) complex

The novel, anti-Markovnikov, arylation of olefins with benzene to produce straight-chain alkylbenzenes with higher selectivity than branched alkylbenzenes is catalyzed by [Ir(μ-acac-O,O′,C³)(acac-O,O′)(acac-C³)]₂ (acac=acetylacetonato), 1 [J. Am. Chem. Soc. 122 (2000) 7414]. The reaction of benzene with propylene gave n-propylbenzene and cumene in 61 and 39% selectivities, respectively. The reaction of benzene and styrene afforded 1,2-diphenylethane in 98% selectivity. Considering the anti-Markovnikov regioselectivity and lack of inhibition by water, we propose that the reaction does not proceed via a Friedel–Crafts, carbocation, mechanism. Complex 1, amongst the various transition metal complexes examined, is the most efficient for catalyzing the anti-Markovnikov olefin arylation. The crystal structure of complex 1 was solved and is consistent with a binuclear Ir(III) structure with three different types of coordinated acac ligands as reported by earlier solution IR and NMR analyses. [Ir(μ-acac-O,O′,C³)(acac-O,O′)Cl]₂, 2, was prepared by the reaction of complex 1 with benzoyl chloride, and the crystal structure was also reported.     

Characterization of polysiloxanes by high-resolution pyrolysis-gas chromatography-mass spectrometry

Summary Thermal degradation of various polysiloxanes was studied by pyrolysis-gas chromatography with a fused silica capillary column. The peak identification was carried out by a directly coupled gas chromatography-mass spectrometry system. Generally, polysiloxanes were thermally degraded to cyclic oligomers along with a small amount of the compounds formed through elimination and/or recombination of the pendent substituents. Most of the degradation products including possible stereo- and structural isomers were completely separated in the high-resolution pyrograms which reflect the original stereoregularities and sequence distributions in the polysiloxane chains. Furthermore, relative peak intensities of the characteristic cyclic oligomers observed were successfully interpreted in terms of the compositions of some kinds of siloxane copolymers.

---

Charakterisierung von Polysiloxanen durch hochauflösende Pyrolyse-GC-MS

---

Dedicated to Prof. Dr. W. Fresenius on the occasion of his 75th birthday     

Any algebraic variety in positive characteristic admits a projective model with an inseparable Gauss map

We determine the values attained by the rank of the Gauss map of a projective model for a fixed algebraic variety in positive characteristic p. In particular, it is shown that any variety in p>0 has a projective model such that the differential of the Gauss map is identically zero. On the other hand, we prove that there exists a product of two or more projective spaces admitting an embedding into a projective space such that the differential of the Gauss map is identically zero if and only if p=2.     

Laser-induced fluorescence spectra of Ne- and Ar -aniline van der waals complexes in supersonic jets. Analysis of rotational structures

Laser-induced fluorescence spectra of Ne- and Ar -aniline complexes were observed with a resolution of 0.04 cm^?1. By a simulation analysis of the rotational structures, the distances between the rare-gas atom and the aromatic ring of aniline were found to be 3.35 ± 0.04 and 3.50 ± 0.04 A in the X?¹A₁ state of the Ne and Ar complexes, respectively, and about 0.05 A shorter when aniline was excited to the ùB₂ state.     

A new synthesis of deglyco-bleomycin A2 aiming at the total synthesis of bleomycin

An improved route to synthesize deglyco-bleomycin A2, the aglycon of bleomycin A2, aiming at the total synthesis of bleomycin is described. The new route is characterized by the stepwise elongation of the amino acid constituents and the use of a thiol ester obtained by aldol condensation.     

Highly diastereoselective 7-endo radical cyclization of ethyl α-methylene-γ-(bromomethyl)dimethylsiloxycarboxylates

The 7-endo radical cyclization of (bromomethyl)dimethylsilyl ethers derived from ethyl γ-hydroxy-α-methylenecarboxylates bearing a bulky γ-substituent such as isopropyl, cyclohexyl, and tert-butyl groups in tetrahydrofuran gave preferentially cyclic silyl ethers bearing the ethoxycarbonyl group anti to the γ-substituents in high yields. Treatment of the cyclic silyl ethers with silica gel gave acyclic ethyl γ-hydroxy-α-[2-(hydroxydimethylsilyl)ethyl]carboxylates. The reduction of the cyclization products with DIBAL followed by Tamao oxidation gave the corresponding acyclic triols.     

Versatile dehydrogenative alcohol silylation catalyzed by Cu(I)-phosphine complex

[reaction: see text] Cu(I) complexes of xanthane-based diphosphines were versatile catalysts for dehydrogenative alcohol silylation, exhibiting high activity and broad substrate scope. Highly selective silylation of 1-decanol over 2-decanol is possible even with a silylating reagent of small steric demand such as HSiMe(2)Ph or HSiEt(3).     

Synthesis of the side chain of a novel carbapenem via iodine-mediated oxidative cyclization of (1R)-N-(1-aryl-3-butenyl)acetamide

A (2R,4S)-trans-disubstituted pyrrolidine ring system was constructed by employing iodine-mediated oxidative cyclization of (1R)-N-[1-(4-bromophenyl)-3-butenyl]acetamide 3 as a key step. The resulting diastereomeric mixture of (2R)-2-aryl-4-acetoxypyrrolidine 4 was stereoselectively converted to the side-chain of a novel ultrabroad-spectrum carbapenem 1, via (2R,4R)-2-aryl-4-hydroxypyrrolidine 7.     

Development of a novel solid-phase extraction element for thermal desorption gas chromatography analysis

A novel solid-phase extraction element is developed for sorptive enrichment of dilute analytes from liquid samples with high extraction efficiencies due to its larger amounts of polydimethylsiloxane (PDMS) absorbent than the conventional syringe type of solid-phase microextraction (SPME). The extraction element is made of titanium (Ti) open tubular tube (30 mm x 1.2 mm i.d. x 1.6 mm o.d.) coated with a chemically bonded layer of PDMS (500 microm in thickness). The extraction element combined with thermal desorption-gas chromatography-mass spectrometry using a pyrolysis-gas chromatography-mass spectrometry system was used to extract and analyze a typical herbicide, bethrodine in water samples over a concentration range from 2.5 to 2.5 x 10(4) ng/l. Thus obtained calibration curve showed good linearity for the tested whole concentration range with regression coefficient of 0.992. Detection limit of 0.5 ng/l level was achieved and the reproducibility of the measurements for bethrodine at 10 ng/l level was found to be fairly good with relative standard deviation below 7.5%.