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1,4-Bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadienes as Strong Salt-Free Reductants for Generating Low-Valent Early Transition Metals With Electron-Donating Ligands

1,4-Bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadienes as Strong Salt-Free Reductants for Generating Low-Valent Early Transition Metals With Electron-Donating Ligands

Teruhiko Saito, Haruka Nishiyama, Hiromasa Tanahashi, Kento Kawakita, Hayato Tsurugi, Kazushi Mashima

J Am Chem Soc. 2014 Apr 2;136(13):5161-70.

PMID: 24597916

Abstract:

Electron-rich organosilicon compounds, such as 1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (2a), 2,5-dimethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (2b), 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (2c), and 1,1'-bis(trimethylsilyl)-1,1'-dihydro-4,4'-bipyridine (4), served as versatile reducing reagents of group 4-6 metal chloride complexes, such as Cp2TiCl2, Cp*2TiCl2 (Cp* = η(5)-C5Me5), Cp*TiCl3, Cp*TaCl4, and WCl4(PMe2Ph)2, to generate the corresponding low-valent metal species in a salt-free manner. Nitrogen-containing reductants, such as 2a-c and 4, had stronger reducing ability than the parent organosilicon reductants, 3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (1a) and 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (1b), as well as a pyridine-derived reductant, 1,4-bis(trimethylsilyl)-1-aza-2,5-cyclohexadiene (3). These greater effects of 2a-c and 4 are likely due to their negative one-electron redox potentials, as typically demonstrated in the reduction of Cp2TiCl2, for which compounds 2a and 4 gave the corresponding one-electron reduced products, pyrazine-bridged and 4,4'-bipyridyl-bridged dimeric Ti(III) complexes 5 and 6, and compounds 2b and 2c afforded the same double chloride-bridged dimeric Ti(III) complex, [Cp2Ti]2(μ-Cl)2 (7), though 1a and 1b could not reduce Cp2TiCl2. Application of the organosilicon compounds as reducing agents for catalytic reactions revealed that the combination of 2c and a catalytic amount of Cp2TiCl2 assisted a Reformatsky reaction of nonanal and ethyl 2-bromoisobutyrate and its derivatives to give ethyl 3-hydroxy-2,2-dimethylundecanoate and its derivatives. In this coupling reaction, 2c served as the best reductant among 2a-c and 4 due to the suppression of an undesired reaction between 2c and ethyl 2-bromoalkanoates.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP1087659253	5-Bromo-3-methoxy-2-(trimethylsilyl)pyridine		1087659-25-3	Price
AP1203498923	2-Chloro-5-methyl-3-(trimethylsilyl)pyridine		1203498-92-3	Price

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