- Iron-Catalyzed Silylation of (Hetero)aryl Chlorides with Et3SiBpin
-
To date, the iron-catalyzed construction of C-heteroatom bonds has been less developed due to the difficulty of transmetalation with heteroatom anions and the sluggish reductive elimination. Herein we report an iron-catalyzed method for the silylation of
- Jia, Jia,Zeng, Xiaoqin,Liu, Zhengli,Zhao, Liang,He, Chun-Yang,Li, Xiao-Fei,Feng, Zhang
-
-
Read Online
- Continuous-flow Si-H functionalizations of hydrosilanesviasequential organolithium reactions catalyzed by potassiumtert-butoxide
-
We herein report an atom-economic flow approach to the selective and sequential mono-, di-, and tri-functionalizations of unactivated hydrosilanesviaserial organolithium reactions catalyzed by earth-abundant metal compounds. Based on the screening of various additives, we found that catalytic potassiumtert-butoxide (t-BuOK) facilitates the rapid reaction of organolithiums with hydrosilanes. Using a flow microreactor system, various organolithiums bearing functional groups were efficiently generatedin situunder mild conditions and consecutively reacted with hydrosilanes in the presence oft-BuOK within 1 min. We also successfully conducted the di-funtionalizations of dihydrosilane by sequential organolithium reactions, extending to a gram-scale-synthesis. Finally, the combinatorial functionalizations of trihydrosilane were achieved to give every conceivable combination of tetrasubstituted organosilane libraries based on a precise reaction control using an integrated one-flow system.
- Lee, Hyune-Jea,Kwak, Changmo,Kim, Dong-Pyo,Kim, Heejin
-
supporting information
p. 1193 - 1199
(2021/02/26)
-
- Silylation of Aryl Chlorides by Bimetallic Catalysis of Palladium and Gold on Alloy Nanoparticles
-
Supported palladium-gold alloy-catalyzed cross-coupling of aryl chlorides and hydrosilanes enabled the selective formation of aryl-silicon bonds. Whereas a monometallic palladium catalyst predominantly promoted the hydrodechlorination of aryl chlorides and gold nanoparticles showed no catalytic activity, gold-rich palladium-gold alloy nanoparticles efficiently catalyzed the title reaction to give arylsilanes with high selectivity. A wide array of aryl chlorides and hydrosilanes participated in the heterogeneously-catalyzed reaction to furnish the corresponding arylsilanes in 34–80% yields. A detailed mechanistic investigation revealed that palladium and gold atoms on the surface of alloy nanoparticles independently functioned as active sites for the formation of aryl nucleophiles and silyl electrophiles, respectively, which indicates that palladium and gold atoms on alloy nanoparticles work together to enable the selective formation of aryl-silicon bonds. (Figure presented.).
- Miura, Hiroki,Masaki, Yosuke,Fukuta, Yohei,Shishido, Tetsuya
-
supporting information
p. 2642 - 2650
(2020/04/22)
-
- C-O Bond Silylation Catalyzed by Iron: A General Method for the Construction of Csp2-Si Bonds
-
The iron-catalyzed construction of Csp2-Si bonds via unreactive C-O bonds possesses a challenging topic in organic chemistry. Herein we report an iron-catalyzed silylation of aryl and alkenyl carbamates via C-O bond activation. This protocol fe
- Zhang, Juan,Zhang, Yun,Geng, Shasha,Chen, Shuo,Liu, Zhengli,Zeng, Xiaoqin,He, Yun,Feng, Zhang
-
supporting information
p. 2669 - 2674
(2020/03/30)
-
- Nickel/copper-cocatalyzed decarbonylative silylation of acyl fluorides
-
Ni/Cu-cocatalyzed decarbonylative silylation of acyl fluorides with silylboranes has been developed to afford various arylsilanes with high efficiency and good functional-group compatibility via carbon-fluorine bond cleavage and carbon-silicon bond formation. Such transformation can not only extend the functionalization type of acyl fluorides but complement the synthetic route for arylsilanes.
- Wang, Xiu,Wang, Zhenhua,Nishihara, Yasushi
-
p. 10507 - 10510
(2019/09/06)
-
- Catalytic reduction of aryl trialkylammonium salts to aryl silanes and arenes
-
A new approach for the reduction of aryl ammonium salts to arenes or aryl silanes using nickel catalysis is reported. This method displays excellent ligand-controlled selectivity based on the N-heterocyclic carbene (NHC) ligand employed. Utilizing a large NHC in non-polar solvents generates aryl silanes, while small NHCs in polar solvents promote reduction to arenes. Several classes of aryl silanes can be accessed from simple aniline building blocks, including those useful for cross-couplings, oxidations, and halogenations. The reaction conditions are mild, functional group tolerant, and provide efficient access to a variety of benzene derivatives.
- Rand, Alexander W.,Montgomery, John
-
p. 5338 - 5344
(2019/05/29)
-
- Arylsilylation of aryl halides using the magnetically recyclable bimetallic Pd-Pt-Fe3O4 catalyst
-
Transition metal-catalyzed silylations have typically involved the use of homogeneous non-recyclable catalytic systems. In this work, the first example of a recyclable catalytic system for the synthesis of arylsilanes has been reported, which utilizes the
- Jang, Jisun,Byun, Sangmoon,Kim, B. Moon,Lee, Sunwoo
-
supporting information
p. 3492 - 3495
(2018/04/09)
-
- Nickel-Catalyzed Decarbonylative Silylation, Borylation, and Amination of Arylamides via a Deamidative Reaction Pathway
-
A nickel-catalyzed decarbonylative silylation, borylation, and amination of amides has been developed. This new methodology allows the direct interconversion of amides to arylsilanes, arylboronates, and arylamines and enables a facile route for carbon-heteroatom bond formations in a straightforward and mild fashion.
- Lee, Shao-Chi,Guo, Lin,Yue, Huifeng,Liao, Hsuan-Hung,Rueping, Magnus
-
p. 2594 - 2598
(2017/10/31)
-
- Intermolecular C-H Silylation of Arenes and Heteroarenes with HSiEt3 under Operationally Diverse Conditions: Neat/Stoichiometric and Acceptor/Acceptorless
-
Efficient protocols for Rh-catalyzed intermolecular C-H silylation of unactivated arenes and heteroarenes are disclosed. The silylations are catalyzed by a Rh-complex (2 mol %) derived in situ from commercially available Rh(nbd)2BF4 and (S,S)-i-Pr-BPE (L3) with Et3SiH in the presence of hydrogen acceptor under either neat (excess of arene) or stoichiometric conditions. The regioselectivity is determined mainly by the steric bulk of the substituents and by the electronic effect as an ancillary factor. In addition, our preliminary result shows that the current protocol catalyzes the silylation of arenes in the absence of hydrogen acceptors.
- Lee, Kang-Sang,Katsoulis, Dimitris,Choi, Jongwook
-
p. 1493 - 1496
(2016/03/15)
-
- Ruthenium-catalyzed c-h silylation of 1-arylpyrazole derivatives and fluoride-mediated carboxylation: Use of two nitrogen atoms of the pyrazole Group
-
Carboxylation of 1-arylpyrazole derivatives was developed using a ruthenium-catalyzed ortho silylation in conjunction with fluoride-mediated carboxylation with carbon dioxide. The two nitrogen atoms of pyrazole play crucial roles in promoting ortho silylation via the formation of a five-membered ruthenacycle and in accelerating aryl anion formation by lowering the electron density of the aromatic ring. Georg Thieme Verlag Stuttgart New York.
- Mita, Tsuyoshi,Tanaka, Hiroyuki,Michigami, Kenichi,Sato, Yoshihiro
-
supporting information
p. 1291 - 1294
(2014/06/10)
-
- Diphenylphosphinite ionic liquid (IL-OPPh2): A solvent and ligand for palladium-catalyzed silylation and dehalogenation reaction of aryl halides with triethylsilane
-
The use of an imidazolium-based phosphinite ionic liquid (IL-OPPh2) as both solvent and ligand for Pd offers an efficient catalytic system for silylation of aryl iodides, bromides and also chlorides by triethylsilane in the presence of Cs2CO3. In the absence of base, this system is also performed for catalytic dehalogenation of aryl halides. The ionic liquid containing its corresponding Pd(0) complex can be easily recovered and reused in several runs without losing its efficiency.
- Iranpoor, Nasser,Firouzabadi, Habib,Azadi, Roya
-
experimental part
p. 887 - 890
(2010/06/16)
-
- Direct and selective arylation of tertiary silanes with rhodium catalyst
-
(Chemical Equation Presented) We have developed a convenient and efficient approach to the arylation of tertiary silanes under mild conditions. A variety of arylsilanes were synthesized in a one-step process with good to excellent yields in the presence of a rhodium catalyst with a base. The reaction was highly solvent dependent, and amides were the most effective of the various solvents used. This common catalyst system is highly tolerant of the various sensitive functional groups on the substrates, which might be difficult to extract by other methods. The rhodium-promoted silylation of aryl halides with electron-donating groups occurred more efficiently than the silylation of aryl halides substituted with electron-withdrawing groups. Heteroaromatic halides were also found to be readily silylated with tertiary silanes. The successful application of this reaction to the synthesis of a TAC-101 analogue, which is a trialkylsilyl-containing synthetic retinoid benzoic acid derivative with selective binding affinity for retinoic acid receptor-α, is also described.
- Yamanoi, Yoshinori,Nishihara, Hiroshi
-
p. 6671 - 6678
(2008/12/22)
-
- Palladium(0)-catalyzed silylation of aryl halides with triorganosilanes: Synthesis of aryl(2-furyl)silanes
-
Triorganosilanes, which possess two aryl groups on the silicon atom, undergo palladium-catalyzed silylation of aryl iodides. Aryl(2-furyl)silanes thus obtained are potentially useful starting materials for carbon-carbon bond-forming reactions in the prese
- Murata, Miki,Ohara, Hiroya,Oiwa, Ryo,Watanabe, Shinji,Masuda, Yuzuru
-
p. 1771 - 1774
(2007/10/03)
-
- Palladium-catalyzed silylations of hydrosilanes with aryl halides using bulky alkyl phosphine
-
A palladium-catalyzed direct trialkylsilyl transfer to aryl halides has been developed. In the presence of Pd(t-Bu3P)2 and K 3PO4, electron-rich para- or meta-substitute aryl iodides were coupled efficiently with triethylsilane, triphenylsilane, and dimethylphenylsilane to afford the corresponding silylated products in moderate to good yields.
- Yamanoi, Yoshinori
-
p. 9607 - 9609
(2007/10/03)
-