Assembly of Enantioenriched cis‐3a,8a‐Hexahydropyrrolo[2,3‐b]indole Scaffolds by Silver(I)‐Catalyzed Asymmetric Domino Reaction of Isocyanoacetates in the Presence of Cinchona‐Derived Chiral Phosphorus Ligands

By using Cinchona‐derived chiral phosphines as catalytic ligands, enantioenriched cis‐3a,8a‐hexahydropyrrolo[2,3‐b]indoles (ent‐HPIs), which are core scaffolds in a large array of biologically active natural products, can be convergently assembled under mild conditions through the silver(I)‐catalyzed asymmetric domino reaction of readily available isocyanoacetates and 2‐(2‐aminophenyl)acrylates. Various functionalities can be tolerated in the reaction, affording enantioenriched HPIs in high overall yields and good enantioselectivities (up to 92% ees).

     

Convergent Activation Concept for CO2 Fixation in Carbonates

Concepts to facilitate the conversion of epoxides with carbon dioxide to the corresponding cyclic carbonates commonly focus on the activation of the epoxide. Herein we report a catalytic system which allows the simultaneous activation of carbon dioxide and the epoxide. This convergent activation concept is realized by combining a suitable carbene as catalyst for the carbon dioxide activation with a second catalytic system based on potassium iodide for epoxide activation. Initial experiments showed synergistic effects and thus proving the feasibility of this activation concept. Moreover a standard protocol was developed and the substrate scope under these conditions has been studied. Under mild and solvent‐free conditions 14 epoxides could be converted. The respective cyclic carbonates were obtained in good to excellent yields with selectivities ≥ 99 % after simple filtration.

     

Palladium and Copper Cocatalyzed Intermolecular Cyclization Reaction: Synthesis of 5‐Aminopyrazole Derivatives

A novel and efficient palladium and copper co‐catalyzed intermolecular cyclization of acetonitriles with hydrazones has been developed for the synthesis of 5‐aminopyrazoles through C C and C N bond formation. The reaction has the advantages of easily available starting materials, simple manipulation and mild reaction conditions. The reaction involving various substituted acetonitriles and hydrazones proceeds smoothly and 5‐aminopyrazoles are synthesized in good yields. In contrast to the aliphatic and heteroaromatic substrates, the aromatic substrates tend to have a higher degree of reactivity.

     

Efficient Metal‐Free Aerobic Photooxidation of Sulfides to Sulfoxides Mediated by a Vitamin B2 Derivative and Visible Light

We have developed a metal‐free process for the aerobic photooxygenation of sulfides to sulfoxides mediated by riboflavin tetraacetate or riboflavin (vitamin B₂) photocatalysts and visible light (450 nm) in an acetonitrile‐water (85:15 v/v) mixture. The optimised solvent system leads to both singlet‐oxygen and electron‐transfer pathways in photooxygenation, thus allowing oxidation of electron‐poor and electron‐rich thioanisoles, dialkyl sulfides and sterically hindered sulfides. Besides having a broad substrate scope, the method has very short reaction times and requires low catalyst loading (down to 0.1 mol%). These properties are due to the high photocatalyst stability and the extremely high quantum yields (1.3 for thioanisole oxygenation). Moreover, the method is chemoselective, producing only sulfoxides without overoxidation to sulfones. Taking into account the broad substrate scope, high selectivity and high efficiency, this method distinguishes itself from those previously reported. Other advantages include easy work‐up of the reaction mixture, the availability and biodegradability of the photocatalysts and mild reaction conditions. We demonstrated, on a preparative scale, its practical application in the synthesis of the psychostimulant modafinil, in the selective oxidation of methionine derivatives, and in the detoxification of mustard gas.

     

Metal‐Free Autoxidative Nitrooxylation of Alkenyl Oximes with Molecular Oxygen

A metal‐free aerobic autoxidative nitrooxylation of alkenyl oximes mediated by tert‐butyl nitrite is described. Molecular oxygen is used as the oxidizing reagent, avoiding use of organic trapping reagents such as 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO). The desired products were obtained in generally high yields.

     

Dearomatization of Indole Derivatives via Palladium‐Catalyzed C?H Bond Functionalization of Pyrroles: Convenient Construction of Spiroindolenines

An intramolecular palladium(II)‐catalyzed dearomative arylation reaction of indoles via C H bond functionalization was developed, providing access to structurally novel spiroindolenines with moderate to good yields. A one‐pot process for the synthesis of spiroindoline derivatives was also realized.

     

Palladium‐Catalyzed Three‐Component Reaction of 3‐(Tri‐n‐ butylstannyl)allyl Acetates,Aldehydes, and Triorganoboranes: An Alternative to the Carbonyl Allylation Using α,γ‐Substituted Allylic Tin Reagents

A three‐component reaction of 3‐(tri‐n‐butylstannyl)allyl acetates, aldehydes, and triorganoboranes in the presence of a palladium‐Xantphos catalyst system predominately gave (E)‐anti‐homoallylic alcohols with high diastereoselectivity and good to high levels of alkene stereocontrol. An efficient chirality transfer was observed when an enantioenriched substrate was employed. The reaction was initiated by the formation of an allylic gem‐palladium/stannyl intermediate, which subsequently underwent allylation of the aldehyde by an allyltributyltin followed by a coupling reaction of the in‐situ‐generated (E)‐vinylpalladium acetate with the triorganoborane.

     

Brandverhalten von Brettsperrholz

Fire behaviour of cross‐laminated timber Cross Laminated Timber (CLT) is currently used in modern timber structures for load‐bearing wall, floor or roof elements as a high quality, innovative and cost‐effective structural element. Careful planning and implementation ensures the safe use of CLT in buildings with increased fire protection requirements and in accordance with the requirements of building‐design standards (e. g. EN 1995‐1‐1 and EN 1995‐1‐2) [1, 2]. Worldwide, many fire tests with CLT have been per‐formed to investigate the influence of different cross‐sectional build‐ups and various adhesives on the fire resistance of CLT floor and wall elements. This paper gives an overview of the extensive investigations, main outcomes are summarized and recommendations on the fire design of CLT elements are given. The investigations show that an adequate data base exists to reliably describe the fire behavior of CLT.     

Sonderlösungen bei der brandschutztechnischen Bewertung von Konstruktionsdetails

Special‐purpose solutions in the fire‐protective evaluation of construction details Very often components or construction details in existing buildings but also in new buildings cannot be evaluated with regard to its fire resistance ability considering established technical building regulations. There are no regulations for the evaluation of such components or construction details as these specific construction details have not been evaluated by a certified test authority. However, these components and construction details very often can be classified in fire resistance classes e. g. by evaluating fire tests, with regard to DIN 4102‐4, on the basis of similar proof of usability or only by pragmatic considerations. Since introducing the technical approval of the fire protection Eurocodes more often engineering methods of fire protection are used based on these Eurocodes by using temperature assessment in order to secure the evaluation results. Within this essay we show methods and ways of fire‐protective evaluation for components and construction details. The approach of proof including dimensions of possible upgrade measurements if necessary are being illustrated by examples of use out of practical experience. At the same time different materials such as steel, concrete and wood will be treated with different fire‐proof products. The essay is to explain ways of evaluation of components and construction details involving fire‐proof requirements including upgrade measurements also especially for existing buildings.