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Keywords = trans-bis-silylation

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13 pages, 899 KiB  
Article
Synthesis of Thiophene-Fused Siloles through Rhodium-Catalyzed Trans-Bis-Silylation
by Akinobu Naka, Maho Inoue, Haruna Kawabe and Hisayoshi Kobayashi
AppliedChem 2024, 4(1), 29-41; https://doi.org/10.3390/appliedchem4010003 - 2 Feb 2024
Viewed by 2176
Abstract
Rhodium-catalyzed reactions of 3-ethynyl-2-pentamethyldisilanylthiophene derivatives (1a1c) have been reported. At 110 °C, compounds 1a1c reacted in the presence of a rhodium complex catalyst, yielding thiophene-fused siloles (2a2c) through intramolecular trans-bis-silylation. To understand [...] Read more.
Rhodium-catalyzed reactions of 3-ethynyl-2-pentamethyldisilanylthiophene derivatives (1a1c) have been reported. At 110 °C, compounds 1a1c reacted in the presence of a rhodium complex catalyst, yielding thiophene-fused siloles (2a2c) through intramolecular trans-bis-silylation. To understand the production of 2a from 1a, the mechanism was investigated using density functional theory (DFT) calculations. Full article
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12 pages, 1675 KiB  
Article
Rhodium-Catalyzed Trans-Bis-Silylation Reactions of 2-Ethynyl-3-pentamethyldisilanylpyridines
by Akinobu Naka and Hisayoshi Kobayashi
Molecules 2023, 28(8), 3284; https://doi.org/10.3390/molecules28083284 - 7 Apr 2023
Cited by 5 | Viewed by 3040
Abstract
Rhodium-catalyzed reactions of 2-ethynyl-3-pentamethyldisilanylpyridine derivatives (1 and 2) are reported. The reactions of compounds 1 and 2 in the presence of catalytic amounts of rhodium complexes at 110 °C gave the corresponding pyridine-fused siloles (3) and (4) [...] Read more.
Rhodium-catalyzed reactions of 2-ethynyl-3-pentamethyldisilanylpyridine derivatives (1 and 2) are reported. The reactions of compounds 1 and 2 in the presence of catalytic amounts of rhodium complexes at 110 °C gave the corresponding pyridine-fused siloles (3) and (4) through intramolecular trans-bis-silylation cyclization. The reaction of 2-bromo-3-(1,1,2,2,2-pentamethyldisilanyl)pyridine with 3-phenyl-1-propyne in the presence of PdCl2(PPh3)2-CuI catalysts afforded 1:2 bis-silylation adduct 6. DFT calculations were also performed to understand the reaction mechanism for the production of compound 3 from compound 1. Full article
(This article belongs to the Special Issue Featured Papers in Organometallic Chemistry)
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