Reductive molybdenum‐catalyzed direct amination of boronic acids with nitro compounds

The synthesis of aromatic amines is of utmost importance in a wide range of chemical contexts. We report a direct amination of boronic acids with nitro compounds to yield (hetero)aryl amines. The novel combination of a dioxomolybdenum(VI) catalyst and triphenylphosphine as inexpensive reductant has revealed to be decisive to achieve this new C-N coupling. Our methodology has proven to be scalable, air and moisture tolerant, highly chemoselective and engages both aliphatic and aromatic nitro compounds. More-over, this general and step-economical synthesis of aromatic secondary amines show cases orthogonality to other aromatic secondary amines show cases orthogonality to other aromatic amine syntheses as it tolerates aryl halides and carbonyl compounds.Junta de Castilla y León (BU022G18),Junta de Castilla y León and FEDER (BU076U16 and BU291P18) and Ministerio de Economía y Competitividad (MINECO) (CTQ2016-75023-C2-1-P

Copper-Catalyzed Synthesis of Alkyl Fluorides, Sterically Hindered Anilines, and 1,4-Dienes

Thesis (Ph.D.)--University of Washington, 2017-08Copper is a versatile transition metal and has been used as a catalyst for constructing a variety of bonds in organic synthesis. It is relatively abundant, cheap, and less toxic than other transition metals, making it an advantageous catalyst. Presented in this thesis are three new copper-catalyzed reactions for the preparation of alkyl fluorides, sterically hindered anilines, and 1,4-dienes. These classes of compounds can be found in nature and have important application in medicinal chemistry and the pharmaceutical industry. Finally, we have also demonstrated the utility of these reactions in the construction of useful organic compounds. Chapter 1 describes the copper-catalyzed fluorination of alkyl triflates for the synthesis of alkyl fluorides. This reaction uses a transition-metal complex as an efficient phase-transfer catalyst under mild reaction conditions. No elimination byproducts were observed when using the optimized reaction conditions. This addresses a long standing issue in alkyl fluoride synthesis. Chapter 2 describes the copper-catalyzed coupling of aryl boronic esters with O-benzoyl hydroxylamines for the synthesis of sterically hindered N,N-dialkyl anilines and N-alkyl anilines. This reaction uses an air stable and commercially available precatalyst and a mild turn over reagent, thus making this reaction a practical method to synthesize anilines. Chapter 3 describes the anti-Markovnikov hydroallylation of terminal alkynes and nonsymmetrical dialkyl substituted alkynes to provide a variety of 1,4-dienes and trisubstituted alkenes. The hydroallylation is syn-stereospecific and highly-regioselective allowing access to stereodefined trisubstituted olefins

Catalytic Anti-Markovnikov Hydroallylation of Terminal and Functionalized Internal Alkynes: Synthesis of Skipped Dienes and Trisubstituted Alkenes

We have developed catalytic anti-Markovnikov hydroallylation of terminal and functionalized internal alkynes. In this article, we describe the development of the reaction, exploration of the substrate scope, and a study of the reaction mechanism. Synthesis of skipped dienes through the hydroallylation of terminal alkyl and aryl alkynes with simple allyl phosphates and 2-substituted allyl phosphates is described. The hydroallylation of functionalized internal alkynes leads to the formation of skipped dienes containing trisubstituted alkenes. We demonstrate that the hydroallylation of internal alkynes can be used in the regio- and diastereoselective synthesis of complex trisubstituted alkenes. A mechanism of the hydroallylation reaction is proposed, and experimental evidence is provided for the key steps of the catalytic cycle. Stoichiometric experiments demonstrate an unexpected role of lithium alkoxide in the carbon–carbon bond-forming step of the reaction. A study of the hydrocupration of internal alkynes provides new insight into the structure, stability, and reactivity of alkenyl copper intermediates, as well as insight into the source of the regioselectivity in reactions of internal alkynes

A feasibility study on cork padding materials

Executive Summary. The feasibility study of Cork Padding Materials was prepared for any interested investors who are willing to invest their resources in the packaging industry. This project study is prepared to discover a new means of generating income, at the same time, maximizing the utilization of agri-wastes. A comprehensive study had been conducted by the proponents, consisting of the technical, marketing, financial, management, as well as the socio-economic aspect. The technical study presents that the product can be produced at the highest quality and at a minimum cost. In addition, the study takes into consideration the manufacturing process, plant size, production schedule, machineries, plant location & layout, utilities, waste disposal, and the labor required. The marketing aspect of the study showed that there is a relatively large demand for padding materials, which is apparently not covered by the existing packaging materials manufacturers. Moreover, the marketing study reflects the results of the survey conducted by the proponents, and among others, the desired market share. Also incorporated in the marketing study are the marketing practices of the competitors and the marketing programs prepared and recommended by the proponents. The management study of the project feasibility reflects the preferred type of business organization for such proposed business undertaking. It also shows the organizational structure appropriate for the business, the flow of business transactions, and the policies in hiring employees. The socio-economic aspect of the study, though may be less comprehensive, contains a very substantial information on how the cork padding business can help the different aspects -- economy, government, social and the environment. The proposed business undertaking can help the government through hiring of employees, payment of taxes, and most importantly, of helping solve the waste problem of our country. The financial aspect of the study quantifies the data obtained in the marketing and technical study. It contains the projected financial statements, ratios, and the financial analysis of the results of business operations and changes in the financial position. As a whole, the study conducted proves that pursuing a business on cork padding materials is feasible in all aspects

Catalytic Anti-Markovnikov Hydroallylation of Terminal and Functionalized Internal Alkynes: Synthesis of Skipped Dienes and Trisubstituted Alkenes

We have developed catalytic anti-Markovnikov hydroallylation of terminal and functionalized internal alkynes. In this article, we describe the development of the reaction, exploration of the substrate scope, and a study of the reaction mechanism. Synthesis of skipped dienes through the hydroallylation of terminal alkyl and aryl alkynes with simple allyl phosphates and 2-substituted allyl phosphates is described. The hydroallylation of functionalized internal alkynes leads to the formation of skipped dienes containing trisubstituted alkenes. We demonstrate that the hydroallylation of internal alkynes can be used in the regio- and diastereoselective synthesis of complex trisubstituted alkenes. A mechanism of the hydroallylation reaction is proposed, and experimental evidence is provided for the key steps of the catalytic cycle. Stoichiometric experiments demonstrate an unexpected role of lithium alkoxide in the carbon–carbon bond-forming step of the reaction. A study of the hydrocupration of internal alkynes provides new insight into the structure, stability, and reactivity of alkenyl copper intermediates, as well as insight into the source of the regioselectivity in reactions of internal alkynes