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Versatile Manganese Catalysis for the Synthesis of Poly(silylether)s from Diols and Dicarbonyls with Hydrosilanes.

ABSTRACT: Poly(silylether)s are interesting materials because of their degradation property under hydrolytic conditions and have been prepared via hydrosilylation polymerization from dicarbonyl and hydrosilanes, and via dehydrogenative cross-coupling of diols and hydrosilanes under catalytic conditions. Here, we present a manganese-salen compound based on an inexpensive and nontoxic metal that could effectively catalyze both polymerization reactions with hydrosilane. A series of poly(silylether)s containing various aliphatic and aromatic backbones have been synthesized from diol and dicarbonyl substrates. Moderate to high yields of polymers with number-average molecular weights up to 15 kg/mol are obtained. Because of the dual activity of the manganese catalyst, unsymmetrical substrates with mixed functional groups, such as p-hydroxybenzaldehyde, p-hydroxy benzylalcohol, and 3-(4-hydroxyphenyl)-1-propanol, have been employed to afford poly(silylether)s with multiple silicon connectivity in the main chain.

SUBMITTER: Vijjamarri S

PROVIDER: S-EPMC6640981 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Diarylamines are an important class of widely utilized chemicals, and development of diverse procedures for their synthesis is of great importance. Herein, we have successfully developed novel versatile catalytic procedures for the synthesis of diarylamines through acceptorless dehydrogenative aromatization. In the presence of a gold-palladium alloy nanoparticle catalyst (Au-Pd/TiO2), various symmetrically substituted diarylamines could be synthesized starting from cyclohexylamines. The observed catalysis of Au-Pd/TiO2 was heterogeneous in nature and Au-Pd/TiO2 could be reused several times without severe loss of catalytic performance. This transformation needs no oxidants and generates molecular hydrogen (three equivalents with respect to cyclohexylamines) and ammonia as the side products. These features highlight the environmentally benign nature of the present transformation. Furthermore, in the presence of Au-Pd/TiO2, various kinds of structurally diverse unsymmetrically substituted diarylamines could successfully be synthesized starting from various combinations of substrates such as (i) anilines and cyclohexanones, (ii) cyclohexylamines and cyclohexanones, and (iii) nitrobenzenes and cyclohexanols. The role of the catalyst and the reaction pathways were investigated in detail for the transformation of cyclohexylamines. The catalytic performance was strongly influenced by the nature of the catalyst. In the presence of a supported gold nanoparticle catalyst (Au/TiO2), the desired diarylamines were hardly produced. Although a supported palladium nanoparticle catalyst (Pd/TiO2) gave the desired diarylamines, the catalytic activity was inferior to that of Au-Pd/TiO2. Moreover, the activity of Au-Pd/TiO2 was superior to that of a physical mixture of Au/TiO2 and Pd/TiO2. The present Au-Pd/TiO2-catalyzed transformation of cyclohexylamines proceeds through complex pathways comprising amine dehydrogenation, imine disproportionation, and condensation reactions. The amine dehydrogenation and imine disproportionation reactions are effectively promoted by palladium (not by gold), and the intrinsic catalytic performance of palladium is significantly improved by alloying with gold. One possible explanation of the alloying effect is the formation of electron-poor palladium species that can effectively promote the ?-H elimination step in the rate-limiting amine dehydrogenation.

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Versatile Manganese Catalysis for the Synthesis of Poly(silylether)s from Diols and Dicarbonyls with Hydrosilanes.

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