Enantioselective Preparation of γ-Amino Acids and γ-Lactams from Nitro Olefins and Carboxylic Acids,with the Valine-Derived 4-Isopropyl-5,5-diphenyl-1,3-oxazolidin-2-one as an Auxiliary

Titanium enolates of acyl-oxazolidinones 1 , derived from acetic, propanoic, 3-methylbutanoic, and 4-methylpentanoic acids and 4-isopropyl-5,5-diphenyl-1,3-oxazolidin-2-one, are added to aliphatic and aromatic nitro olefins in the presence of TiCl₄ (Schemes 2 – 4). The products, 4-nitro carboxylic-acid derivatives 2 , are formed in high diastereoselectivities (ds 80 to >99%) and in good yields (50 – 75% of purified samples of ds >98%). Hydrogenation over Raney-Ni of the NO₂ group in the adducts leads directly to the corresponding γ-lactams ( 3 and 8 ; 80 – 92%), with recovery of the insoluble auxiliary (ca. 95%). Ring opening is achieved through the N-Boc-lactams ( 4 ), which are converted to N-Boc-protected γ-amino acids 5 or to their benzyl and methyl esters ( 6 and 7 ; Scheme 5). The configuration of the products (containing up to three new stereogenic centers; Scheme 1) is assigned by comparison with literature data, by X-ray crystal-structure analysis (for 2c , g , f , 8 , Fig.), and by analogy. Thus, the (S)-auxiliary gives rise to combination of the trigonal centers of enolate and nitro olefin with Si/Si topicity (relative topicity all-lk; cf. A ).     

EFFECT OF METAL IONS ON THE LUMINESCENCE OF ACRIDINE DYES BOUND TO DNA

Abstract— The luminescence of acridine dyes intercalated in DNA was studied as a function of the concurrent binding of metal ions to DNA, in an effort to deduce specific site interactions of the dyes. Two dyes, proflavine (PF) and acridine orange (AO), and two metal ions, silver and mercuric, were used. Both ions quench the fluorescence of the dyes in aqueous solution at room temperature. The metal ions have a different effect on the fluorescence of these dyes when they are intercalated between the base pairs of DNA. The fluorescence of AO is decreased when silver is bound, while the fluorescence of PF is enhanced. Since Ag⁺ initially binds to GC sites in DNA, which quench the PF fluorescence, it ostensibly 'turns off' the quenching by DNA at these sites, and this effect is greater than the quenching effect of the silver ion itself. Hg²⁺ ion initially binds to AT sites in DNA. Since both dyes fluoresce from AT sites, Hg²⁺ is expected to quench their fluorescence. This behavior is observed at low r (metal ion/base). At higher r values, however, where Hg²⁺ is expected to begin binding to GC sites, the fluorescence of PF is enhanced. These quenching turn-off effects are tentatively interpreted in terms of a change in the structure of the dye/DNA complex which occurs when a metal ion binds at the intercalation site. At 77 K. no fluorescence enhancement is observed when metal ions bind; Ag⁺ quenches the fluorescence and enhances the phosphorescence of both dyes. Qualitatively similar results are obtained with Hg²⁺.     

Korrosion und Schutzanstriche

Ohne Zusammenfassung     

Korrosionsuntersuchung

Ohne Zusammenfassung     

β-N-Heterocyclic Cyclobutane Carboximides: Synthesis through a Tandem Base-Catalyzed Amidation/aza-Michael Addition Protocol and Facile Transformations

A stereoselective one-pot double derivatization of cyclobutene-1-carboxylic acid via a mild organic base catalyzed amidation/aza-Michael addition of benzo[d]oxazol-2(3H)-ones has been developed. This unprecedented tandem reaction provides access to novel β-N-heterocyclic cyclobutane carboximide derivatives with a trans geometry. The carboximide moiety reacts smoothly with nucleophiles, allowing access to diverse derivatives of trans-β-N-heterocyclic cyclobutanecarboxylic acid, including peptidomimetic structures.     

trans-[Pt(BCat')Me(PCy3)2]: an experimental case study of reductive elimination processes in Pt-Boryls through associative mechanisms

A stable trans‐(alkyl)(boryl) platinum complex trans‐[Pt(BCat′)Me(PCy₃)₂] (Cat′=Cat‐4‐tBu; Cy=cyclohexyl=C₆H₁₁) was synthesised by salt metathesis reaction of trans‐[Pt(BCat′)Br(PCy₃)₂] with LiMe and was fully characterised. Investigation of the reactivity of the title compound showed complete reductive elimination of Cat′BMe at 80 °C within four weeks. This process may be accelerated by the addition of a variety of alkynes, thereby leading to the formation of the corresponding η²‐alkyne platinum complexes, of which [Pt(η²‐MeCCMe)(PCy₃)₂] was characterised by X‐ray crystallography. Conversion of the trans‐configured title compound to a cis derivative remained unsuccessful due to an instantaneous reductive elimination process during the reaction with chelating phosphines. Treatment of trans‐[Pt(BCat′)Me(PCy₃)₂] with Cat₂B₂ led to the formation of CatBMe and Cat′BMe. In the course of further investigations into this reaction, indications for two indistinguishable reaction mechanisms were found: 1) associative formation of a six‐coordinate platinum centre prior to reductive elimination and 2) σ‐bond metathesis of B? B and C? Pt bonds. Mechanism 1 provides a straightforward explanation for the formation of both methylboranes. Scrambling of diboranes(4) Cat₂B₂ and Cat′₂B₂ in the presence of [Pt(PCy₃)₂], fully reductive elimination of CatBMe or Cat′BMe from trans‐[Pt(BCat′)Me(PCy₃)₂] in the presence of sub‐stoichiometric amounts of Cat₂B₂, and evidence for the reversibility of the oxidative addition of Cat₂B₂ to [Pt(PCy₃)₂] all support mechanism 2, which consists of sequential equilibria reactions. Furthermore, the solid‐state molecular structure of cis‐[Pt(BCat)₂(PCy₃)₂] and cis‐[Pt(BCat′)₂(PCy₃)₂] were investigated. The remarkably short B? B separations in both bis(boryl) complexes suggest that the two boryl ligands in each case are more loosely bound to the Pt^II centre than in related bis(boryl) species.     

The protective role of melanin against UV damage in human skin

Human skin is repeatedly exposed to UVR that influences the function and survival of many cell types and is regarded as the main causative factor in the induction of skin cancer. It has been traditionally believed that skin pigmentation is the most important photoprotective factor, as melanin, besides functioning as a broadband UV absorbent, has antioxidant and radical scavenging properties. Besides, many epidemiological studies have shown a lower incidence for skin cancer in individuals with darker skin compared to those with fair skin. Skin pigmentation is of great cultural and cosmetic importance, yet the role of melanin in photoprotection is still controversial. This article outlines the major acute and chronic effects of UVR on human skin, the properties of melanin, the regulation of pigmentation and its effect on skin cancer prevention.     

An additive analysis of multiplicative Schwarz methods

We present an analysis of multiplicative Schwarz methods for symmetric positive definite problems that is based on the theory of additive Schwarz preconditioners and discuss applications to multigrid methods and domain decomposition methods.