Synthesis of aryltriethoxysilanes via rhodium(I)-catalyzed cross-coupling of aryl electrophiles with triethoxysilane

Murata, Miki; Yamasaki, Hiyoruki; Ueta, Tsukasa; Nagata, M.; Ishikura, Masanori; Watanabe, Shuichi; Masuda, Yoshio

doi:10.1016/j.tet.2007.02.103

Cited by 53 publications

(22 citation statements)

References 54 publications

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“…Discouragingly, in this work, neither of these specific protocols allowed the preparation of (1 E ,3 E )‐dienylsilanes 8 from iodide 11 or of (1 Z ,3 E )‐dienylsilanes 9 from iodide 12 ; only starting materials or complex reaction mixtures were obtained (Table 2). The same dissuasive results were provided by several conditions previously reported for silylation of aryl halides by using platinum (Me 2 EtOSiH, PtO 2 , AcONa, NMP)31j or rhodium (Me 2 EtOSiH, [{RhCl(cod)} 2 ], Et 3 N, DMF) 31i…”

Section: Resultssupporting

confidence: 82%

Cross‐Coupling Reactions of Organosilicon Compounds in the Stereocontrolled Synthesis of Retinoids

Bergueiro

Montenegro

Cambeiro

et al. 2012

Chemistry A European J

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This paper presents a full account of the use of Hiyama cross-coupling reactions in a highly convergent approach to retinoids in which the key step is construction of the central C10-C11 bond. Representatives of two families of oxygen-activated dienyl silanes (ethoxysilanes and silanols) and of all reported families of "safety-catch" silanols (siletanes, silyl hydrides, allyl-, benzyl-, aryl-, 2-pyridyl- and 2-thienylsilanes) were regio- and stereoselectively prepared and stereospecifically coupled to an appropriate electrophile by treatment with a palladium catalyst and a nucleophilic activator. Both all-trans and 11-cis-retinoids, and their chain-demethylated analogues, were obtained in good yields regardless of the geometry (E/Z) and of the steric congestion in each fragment. This comprehensive study conclusively establishes the Hiyama cross-coupling reaction, with its mild reaction conditions and stable, easily prepared, ecologically advantageous silicon-based coupling partners, as the most effective route to retinoids reported to date.

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Section: Resultssupporting

confidence: 82%

Cross‐Coupling Reactions of Organosilicon Compounds in the Stereocontrolled Synthesis of Retinoids

Bergueiro

Montenegro

Cambeiro

et al. 2012

Chemistry A European J

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“…13 For molecules that contain functional groups that are not compatible with Grignard reagents, Pd(0)- or Rh(I)-catalyzed silylation of aryl iodides and bromides with tetraethoxysilanes can afford aryl silanes. 14 …”

Section: Introductionmentioning

confidence: 99%

Silver-mediated fluorination of aryl silanes

2011

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“…On the other hand, it is worth noting that the thienyl group was introduced in moderate yield by utilizing the Pd catalyst (run 6), whereas the Rh catalyst did not work for 3j (Run 11 in Table ). This result corresponds to the case of arylation of triethoxysilane, though the reason remains to be clear. It has been demonstrated that adequate selection from the present Rh and Pd catalysts can expand the scope of applicable substrates.…”

Section: Resultsmentioning

confidence: 63%

Transition‐Metal‐Catalyzed Direct Arylation of Caged Silsesquioxanes: Substrate Scope and Mechanistic Study

et al. 2019

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Caged silsesquioxane (polyhedral oligomeric silsesquioxane: POSS) is an important class of organic‐inorganic hybrid molecules. The electronic properties of POSS have gradually attracted attention from experimental and computational perspectives, while POSS is generally utilized for reinforcement of polymer materials. Practical synthetic routes to access to aryl‐substituted POSS are effective tools for the systematic studies. Recently, we reported Rh‐catalyzed direct arylation of heptaisobutyl‐POSS with electron‐rich aryl iodides. Herein substrates for the Rh‐catalyzed direct arylation were widely examined: electron‐deficient, sterically‐hindered, and heteroatom‐containing aryl halides, and heptaphenyl‐POSS. Pd‐catalyzed direct arylation of POSS was developed as well. Notably, thiophene was introduced by the Pd‐catalyst, whereas the Rh‐system did not work for the substrate. In addition, the reaction mechanism of the Rh‐catalyzed reaction was elucidated by density functional theory calculations.

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Synthesis of aryltriethoxysilanes via rhodium(I)-catalyzed cross-coupling of aryl electrophiles with triethoxysilane

Cited by 53 publications

References 54 publications

Cross‐Coupling Reactions of Organosilicon Compounds in the Stereocontrolled Synthesis of Retinoids

Cross‐Coupling Reactions of Organosilicon Compounds in the Stereocontrolled Synthesis of Retinoids

Silver-mediated fluorination of aryl silanes

Transition‐Metal‐Catalyzed Direct Arylation of Caged Silsesquioxanes: Substrate Scope and Mechanistic Study

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