Synthesis of Densely Functionalized Cyclopropanes via Diastereoselective Nucleophilic Additions to in Situ Generated Cyclopropenes

This thesis is concerned with the development and application of methods for the diastereoselective synthesis of substituted cyclopropanes. The methodology described in this dissertation is based on the addition of nucleophiles to highly reactive cyclopropene intermediates, to which a variety of oxygen and nitrogen-based nucleophiles can be efficiently employed in this transformation. The presented methodology provides easy access to di-, tri- and tetrasubstituted cyclopropanes which is divided into three chapters and describes not only the methodology developed in our research group but also other synthetic routes to densely substituted cyclopropanes. Chapter one is a review of synthetic methodologies for the preparation of densely substituted chirally-rich cyclopropanes with three stereocenters. The first part of the chapter will describe the stereoselective addition of zinc carbenoids to substituted alkenes. The following section will cover recent advances in the field of transition-metal-catalyzed carbene chemistry. Other methods including Michael-initiated ring closure and C-H activation reactions will be discussed in the final part of chapter one. Chapter two focuses on intermolecular formal nucleophilic substitution of bromocyclopropanes with azoles and anilines. The developed methodology aims for the construction of stereodefined di- and trisubstituted cyclopropanes. Formal substitution of bromocyclopropanes proceeds via the dehydrohalogenation of bromocyclopropane generating cyclopropene in situ followed by subsequent addition of a nitrogen-based nucleophile with efficient selectivity control achieved by thermodynamically driven epimerization of enolizable carboxamides or directing effect of a substituent on a three-membered cycle. Chapter three describes a highly efficient and diastereoselective synthesis of tetrasubstituted donor-acceptor cyclopropanes that can be obtained in a homochiral form from corresponding bromocyclopropyl carboxylic acids. A single chiral center on bromocyclopropane dictates the configuration of the other two stereocenters that are successively installed via a sterically controlled addition of a nucleophile to a chiral trisubstituted cyclopropene, followed by a thermodynamically driven epimerization of the resulting enolate intermediate. This new "dual-control" strategy was successfully employed to the synthesis of densely substituted cyclopropanes in inter- and intramolecular fashion

Preparation of Chiral Enantioenriched Densely Substituted Cyclopropyl Azoles, Amines, and Ethers via Formal SN2′ Substitution of Bromocylopropanes

Enantiomerically enriched cyclopropyl ethers, amines, and cyclopropylazole derivatives possessing three stereogenic carbon atoms in a small cycle are obtained via the diastereoselective, formal nucleophilic substitution of chiral, non-racemic bromocyclopropanes. The key feature of this methodology is the utilization of the chiral center of the cyclopropene intermediate, which governs the configuration of the two adjacent stereocenters that are successively installed via 1,4-addition/epimerization sequence

Supply Chain Management of Industrial Enterprise Based on the Participation in Network Architecture Holdings (Case Study: SPV)

Abstract— The modern industry of the Russian Federation is experiencing an acute shortage of long-term investment resources for technological re-equipment programs aimed at import substitution. The purpose of the study is to identify topical issues of the supply chain management at an industrial enterprise that has become an SPV in a business network. The study is mainly based on the methodology for modeling supply chain management of the recipient enterprise and the method of discounting its cash flows generated with the participation of the industrial enterprise in the leasing process. The proposed concept of systematic management of the leasing process based on business networks allows investors to focalize investment resources on the basis of a set of management methods in order to accelerate the launch of industrial production and increase capitalization. The proposed systematic supply chain management concept is of practical value for a wide range of organizations considering the possibility of using tools for technological re-equipment of industrial production in the context of platform-based business networks. Implementation of the supply chain in SPV is showed at creation of a continuous innovations flow, reduction of technological development costs and unfirming system for development

Cascade Synthesis of Pyrroles from Nitroarenes with Benign Reductants Using a Heterogeneous Cobalt Catalyst

A bifunctional 3d-metal catalyst for the cascade synthesis of diverse pyrroles from nitroarenes is presented. The optimal catalytic system Co/NGr-C@SiO2-L is obtained by pyrolysis of a cobalt-impregnated composite followed by subsequent selective leaching. In the presence of this material, (transfer) hydrogenation of easily available nitroarenes and subsequent Paal–Knorr/Clauson-Kass condensation provides >40 pyrroles in good to high yields using dihydrogen, formic acid, or a CO/H2O mixture (WGSR conditions) as reductant. In addition to the favorable step economy, this straightforward domino process does not require any solvents or external co-catalysts. The general synthetic utility of this methodology was demonstrated on a variety of functionalized substrates including the preparation of biologically active and pharmaceutically relevant compounds, for example, (+)-Isamoltane. © 2020 The Authors. Published by Wiley-VCH Gmb

Intermetallic nickel silicide nanocatalyst—A non-noble metal–based general hydrogenation catalyst

Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO2 as the silicon atom source. The process involves thermal reduction of Si–O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon–carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal–based catalysts

Eco-Economic Security of the Region: Expanding the Management System for Assessing the State of Development

Abstract- The problem of ensuring environmental and economic security for quite a long time remains relevant in the world community. It is the subject of continual scientific debates. The alignment of IT strategy which is a necessity. Information technology is useful for companies when they can be used in the right way. In this regard, learning can be an effective step in transferring knowledge to human and financial management. Unfortunately, in many cases the priority in strategic planning, namely in the mechanisms for implementing the existing strategies, is given to the interests of large manufacturers, whose goals (increase in profits, business costs, etc.) are often diametrically opposed to socio-ecological goals (for example, decrease of harmful emissions through spending more money on treatment plants in order to prevent natural degradation and morbidity of the population, etc.). The solution of this problem should be based on the concept of balanced eco-economic development and changes in the paradigm of entrepreneurship education. It is very important that any economic project is environmentally sound, and any environmental decision is economically feasible. At the same time every environmental decision should take into account the development of the well-being of citizens and the development of the region. All this requires the development of a whole system of stimulating the social and environmental responsibility of contaminating plants, both at the level of the state as a whole and at the regional level. In Russia, scientific research on this issue has been actively conducted for 10-15 years. Based on this research, some standard methods for assessing the eco-economic development of the territories were developed. However, in the context of current conditions, they need radical changes and new approaches. Let us consider this problem in more detail

Cascade Synthesis of Pyrroles from Nitroarenes with Benign Reductants Using a Heterogeneous Cobalt Catalyst

A bifunctional 3d-metal catalyst for the cascade synthesis of diverse pyrroles from nitroarenes is presented. The optimal catalytic system Co/NGr-C@SiO2-L is obtained by pyrolysis of a cobalt-impregnated composite followed by subsequent selective leaching. In the presence of this material, (transfer) hydrogenation of easily available nitroarenes and subsequent Paal–Knorr/Clauson-Kass condensation provides >40 pyrroles in good to high yields using dihydrogen, formic acid, or a CO/H2O mixture (WGSR conditions) as reductant. In addition to the favorable step economy, this straightforward domino process does not require any solvents or external co-catalysts. The general synthetic utility of this methodology was demonstrated on a variety of functionalized substrates including the preparation of biologically active and pharmaceutically relevant compounds, for example, (+)-Isamoltane. © 2020 The Authors. Published by Wiley-VCH Gmb

Formal Nucleophilic Substitution of Bromocyclopropanes with Azoles

A highly diastereoselective protocol for the formal nucleophilic substitution of 2-bromocyclopropylcarboxamides with azoles is described. A wide range of azoles, including pyrroles, indoles, benzimidazoles, pyrazoles, and benzotriazoles, can be efficiently employed as pronucleophiles in this transformation, providing expeditious access to <i>N</i>-cyclopropyl heterocycles

Templated Assembly of Chiral Medium-Sized Cyclic Ethers via 8‑endo-trig Nucleophilic Cyclization of Cyclopropenes

An efficient approach toward enantioenriched eight-membered heterocycles via the intramolecular formal substitution of bromocyclopropanes with oxygen-based nucleophiles has been developed. The reaction proceeds via a reactive cyclopropene intermediate, which undergoes a rapid 8-<i>endo-trig</i> cyclization affording <i>cis</i>-fused [6.1.0] bicyclic products exclusively. The quaternary chiral center in the cyclopropene governs the configuration of the other two stereocenters in the final product