Post‐Grignard Reagents: Influence of the Coligands L on the Molecular Structures of Phenylcalcium Iodides [(L)nCa(R)I] and Calcium Diiodides [(L)nCaI2]

Iodide is a very soft and large anion and as such its extreme ability to be polarized leads to a flat energy surface with respect to the variation of the Ca–I distances in [(L)_nCaI₂] and [(L)_nCa(R)I]. The influence of the donor strength and the bulkiness of the neutral coligands L on the Ca–I distances is studied. The base adducts of calcium diiodide can be isolated after the addition of L to CaI₂ or from the Schlenk equilibrium after the direct synthesis of calcium powder with aryl iodides. As L the ethers diethyl ether (Et₂O), tetrahydrofuran (thf), tetrahydropyran (thp), 1,2‐dimethoxyethane (dme), 18‐crown‐6 (18C6), bis(methoxyethyl)ether (diglyme), and amines tetramethylethylenediamine (tmeda), and hexamethyltriethylenetetramine (hmteta) are studied yielding the adducts [(thp)₄Ca(Ph)I] ( 1a ), [(thf)₄Ca(Ph)I] ( 1b ), [(dme)₂(thf)Ca(Ph)I] ( 1c ), [(18C6)Ca(Ph)I] ( 1d ), and [(tmeda)₂Ca(Ph)I] ( 1e ), as well as [(thp)₄CaI₂] ( 2a ), [(thf)₄CaI₂] ( 2b ), [(Et₂O)₄CaI₂] ( 2c ), [(diglyme)(thf)₂CaI₂] ( 2d ), [(diglyme)(dme)CaI₂] ( 2e ), [(dme)₂(thf)CaI₂] ( 2f ), [(18C6)CaI₂] ( 2g ), [(tmeda)₂CaI₂] ( 2h ), and [(hmteta)CaI₂] ( 2i ). For comparison reasons, [(thf)₄Ca(Ph)Br] ( 3a ), [(thp)₄CaBr₂] ( 4a ), [(thf)₄CaBr₂] ( 4b ), and [(dme)₂(AcOH)CaBr₂] ( 4c ) with AcOH being acetic acid are included as well. The comparison shows that the coordination number of calcium itself only plays an insignificant role whereas bulkiness and donor strength of L represent the key influences.     

A general strategy for the synthesis of difluoromethyl-containing pyrazoles, pyridines and pyrimidines

Difluoromethyl-containing heteroannulated pyridines, pyrimidines and pyrazoles are prepared by a two step method. The regioselective cyclizations of electron-excessive aminoheterocycles, hydrazines and amidines with CF₂Cl-substituted 1,3-dicarbonyl compounds provide the corresponding CF₂Cl-substituted heterocycles. Subsequent radical reactions with trimethylstannane or allyltrimethylstannane gave difluoromethyl-containing heteroannulated pyridines, pyrimidines and pyrazoles, respectively.     

Site-selective Suzuki cross-coupling reactions of 2,3-dibromobenzofuran

The Suzuki-Miyaura reaction of 2,3-dibromobenzofuran with two equivalents of boronic acids gave 2,3-diarylbenzofurans. The reaction with one equivalent of arylboronic acids resulted in site-selective formation of 2-aryl-3-bromobenzofurans. 2,3-Diarylbenzofurans containing two different aryl groups were prepared from 2,3-dibromobenzofuran in a one-pot protocol by sequential addition of two different boronic acids.     

On M. G. Krein's papers in the theory of spaces with an indefinite metric

This is a survey of the papers by M. G. Krein (and his disciples) devoted to the theory of operators in spaces with an indefinite metric and its applications.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 46, Nos. 1–2, pp. 5–17, January–February, 1994.     

Synthesis of 2‐Unsubstituted 1,3‐Selenazoles by Cyclization of Selenoformamide with α‐Bromocarbonyl Compounds

2‐Unsubstituted 1,3‐selenazoles were prepared by cyclization of selenoformamide with α‐bromoacetophenones. Parent 1,3‐selenazole was prepared by cyclization of selenoformamide with α‐bromoacetaldehyde.     

Synthesis of Arylated Benzofurans by Regioselective Suzuki–Miyaura Cross‐Coupling Reactions of 2,3‐Dibromobenzofurans‐ and 2,3,5‐Tribromobenzofurans

Arylated benzofurans were prepared by regioselective Suzuki–Miyaura cross‐coupling reactions of 2,3‐dibromobenzofuran. The reactions proceeded with very good site‐selectivity in favor of the more electron deficient position 2. The Suzuki–Miyaura reactions of 2,3,5‐tribromobenzofuran also proceeded in favor of position 2.     

Unexpected Ring Enlargement of 2‐Hydrazono‐2,3‐dihydro‐1,3‐thiazoles to 1,3,4‐Thiadiazines

The cyclization of thiosemicarbazide with α‐bromoacetophenone can result in the formation of isomeric 1,3,4‐thiadiazines and two different thiazoles. We studied the use of 4‐methyl‐ and 4‐ethylthiosemicarbazide as dinucleophilic building blocks. In this context, we observed an unprecedented rearrangement of a 2‐hydrazono‐2,3‐dihydrothiazole to a 1,3,4‐thiadiazine. While ring contractions of 1,3,4‐thiadiazines to thiazoles are quite common, ring enlargements are new. The course of the reaction depends on the substitution pattern of the substrate.     

Cyclization of 4‐Phenylthiosemicarbazide with Phenacylbromide Revisited. Formation of 1,3,4‐Thiadiazines and of Isomeric 1,3‐Thiazoles

The cyclization of 4‐phenylthiosemicarbazide with phenacylbromide, carried out in refluxing ethanol, afforded 1,3,4‐thiadiazine 1 as the major product. In contrast to a previous report, 2‐phenylimino‐4‐phenyl‐2,3‐dihydro‐1,3‐thiazol‐3‐amine ( 2 ) and not 2‐hydrazono‐3,4‐diphenyl‐2,3‐dihydro‐1,3‐thiazole ( 8 ) was formed as a side‐product. This product is the main product when the reaction is carried out in concentrated hydrochloric acid. Our findings were independently confirmed by independent syntheses of the isomeric products and by a thorough study of their reactivity. It is important to note that the product distribution of the cyclization of thiosemicarbazides with haloketones strongly depends on the substitution pattern and on the reaction conditions.     

Dual-primal isogeometric tearing and interconnecting solvers for multipatch continuous and discontinuous Galerkin IgA equations

We present results regarding fast and robust solvers for equations arising from continuous and discontinuous Galerkin discretization of heterogeneous diffusion problems in the context of Isogeometric Analysis. The solvers considered belong to the class of non-overlapping domain decomposition methods which use tearing and interconnection strategies. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Responsive microgrooves for the formation of harvestable tissue constructs

Given its biocompatibility, elasticity, and gas permeability, poly(dimethylsiloxane) (PDMS) is widely used to fabricate microgrooves and microfluidic devices for three-dimensional (3D) cell culture studies. However, conformal coating of complex PDMS devices prepared by standard microfabrication techniques with desired chemical functionality is challenging. This study describes the conformal coating of PDMS microgrooves with poly(N-isopropylacrylamide) (PNIPAAm) by using initiated chemical vapor deposition (iCVD). These microgrooves guided the formation of tissue constructs from NIH-3T3 fibroblasts that could be retrieved by the temperature-dependent swelling property and hydrophilicity change of the PNIPAAm. The thickness of swollen PNIPAAm films at 24 °C was approximately 3 times greater than at 37 °C. Furthermore, PNIPAAm-coated microgroove surfaces exhibit increased hydrophilicity at 24 °C (contact angle θ = 30° ± 2) compared to 37 °C (θ = 50° ± 1). Thus PNIPAAm film on the microgrooves exhibits responsive swelling with higher hydrophilicity at room temperature, which could be used to retrieve tissue constructs. The resulting tissue constructs were the same size as the grooves and could be used as modules in tissue fabrication. Given its ability to form and retrieve cell aggregates and its integration with standard microfabrication, PNIPAAm-coated PDMS templates may become useful for 3D cell culture applications in tissue engineering and drug discovery.