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Gold(I)-Catalyzed Aromatization: Expeditious Synthesis of Polyfunctionalized Naphthalenes.

ABSTRACT: A gold-catalyzed 6-endo-dig carbocyclization of alkyne with the pendent diazo group is reported. It provides an expeditious approach for the synthesis of multi-functionalized naphthalene derivatives under mild conditions. Mechanistic studies suggest that a vinyl gold carbene is generated as the key intermediate in this cascade transformation that smoothly delivers naphthalene products through an unprecedented stepwise aromatization or an intermolecular aromatic substitution process. The unique endocyclic vinyl species is inaccessible with other precursors; thus, novel carbene cascade transformations could be envisioned with the current catalytic model. Functional groups, such as alkenyl, hydroxyl, amino, and carboxyl groups, remain untouched under these conditions. In addition, the utility of these generated 2-carboxyl naphthalenes is illustrated by the synthesis of chiral 1,2'-binaphthalene ligands and ?-conjugated polycyclic hydrocarbons (CPHs).

SUBMITTER: Zhang C

PROVIDER: S-EPMC6849331 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

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Gold(I)-Catalyzed Aromatization: Expeditious Synthesis of Polyfunctionalized Naphthalenes.

Zhang Cheng C Hong Kemiao K Dong Shanliang S Pei Chao C Zhang Xiaolu X He Ciwang C Hu Wenhao W Xu Xinfang X

iScience 20191025

A gold-catalyzed 6-endo-dig carbocyclization of alkyne with the pendent diazo group is reported. It provides an expeditious approach for the synthesis of multi-functionalized naphthalene derivatives under mild conditions. Mechanistic studies suggest that a vinyl gold carbene is generated as the key intermediate in this cascade transformation that smoothly delivers naphthalene products through an unprecedented stepwise aromatization or an intermolecular aromatic substitution process. The unique e ...[more]

PMID: 31710965

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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 β-H elimination step in the rate-limiting amine dehydrogenation.

Dataset Information

Gold(I)-Catalyzed Aromatization: Expeditious Synthesis of Polyfunctionalized Naphthalenes.

Publications

Gold(I)-Catalyzed Aromatization: Expeditious Synthesis of Polyfunctionalized Naphthalenes.

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