- Intermolecular and intramolecular, platinum-catalyzed, acceptorless dehydrogenative coupling of hydrosilanes with aryl and aliphatic methyl C-H bonds
-
Intermolecular acceptorless dehydrogenative coupling of silanes with arene C-H bonds and intramolecular coupling of silanes with aryl and alkyl C-H bonds occur in good yield in the presence of 5 mol % of TpMe2PtMe2H (Tpsu
- Tsukada, Naofumi,Hartwig, John F.
-
-
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)
-
- 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
-
supporting information
p. 2816 - 2821
(2020/03/30)
-
- A mild and ligand-free Ni-catalyzed silylation via C-OMe cleavage
-
Metal-catalyzed transformations that forge carbon-heteroatom bonds are of central importance in organic synthesis. Despite the formidable potential of aryl methyl ethers as coupling partners, the scarcity of metal-catalyzed C-heteroatom bond formations via C-OMe cleavage is striking, with isolated precedents requiring specialized, yet expensive, ligands, high temperatures, and π-extended backbones. We report an unprecedented catalytic ipso-silylation of aryl methyl ethers under mild conditions and without recourse to external ligands. The method is distinguished by its wide scope, which includes the use of benzyl methyl ethers, vinyl methyl ethers, and unbiased anisóle derivatives, thus representing a significant step forward for designing new C-heteroatom bond formations via C-OMe scission. Applications of this transformation in orthogonal silylation techniques as well as in further derivatizations are also described. Preliminary mechanistic experiments suggest the intermediacy of Ni(0)-ate complexes, leaving some doubt that a canonical catalytic cycle consisting of an initial oxidative addition of the C-OMe bond to Ni(0) species comes into play.
- Zarate, Cayetana,Nakajima, Masaki,Martin, Ruben
-
supporting information
p. 1191 - 1197
(2017/05/16)
-
- 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)
-
- Regiocontrolled cobalt-catalyzed Diels-Alder reactions of silicon-functionalized, terminal, and internal alkynes
-
(Chemical Equation Presented) The efficient control of the regiochemistry of the Diels-Alder adducts which are formed in excellent yields from 1,3-dienes and alkynylsilanes can be realized utilizing cobalt complexes with a pyridine-imine ligand or a dppe ligand, respectively. The application of 2-trimethylsilyloxy-1,3-butadiene leads to a very interesting cyclohexenone derivative suitable for further transformations.
- Hilt, Gerhard,Janikowski, Judith
-
supporting information; experimental part
p. 773 - 776
(2009/08/19)
-
- 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)
-
- Development of Odorless Thiols and Sulfides and Their Applications to Organic Synthesis
-
Development of new odorless thiols (dodecanethiol, 4-n- heptylphenylmethanethiol, 4-trimethylsilylphenylmethanethiol, 4-trimethylsilylbenzenethiol) and an odorless sulfide (1-methylsulfanyldodecane) and their applications to dealkylation, Michael addition, Swern oxidation, and Corey-Kim oxidation are described.
- Nishide, Kiyoharu,Ohsugi, Shin-Ichi,Miyamoto, Tetsuo,Kumar, Kamal,Node, Manabu
-
p. 189 - 200
(2007/10/03)
-
- Synthetic equivalents of benzenethiol and benzyl mercaptan having faint smell: Odor reducing effect of trialkylsilyl group
-
Syntheses and odor tests of the trialkylsilylated benzyl mercaptans and benzenethiols have revealed that the trimethylsilyl substituent on the benzene ring has a remarkable effect in reducing the foul smell of the parent benzyl mercaptan and benzenethiol.
- Nishide, Kiyoharu,Miyamoto, Tetsuo,Kumar, Kamal,Ohsugi, Shin-Ichi,Node, Manabu
-
p. 8569 - 8573
(2007/10/03)
-
- Catalytic C-H Activation. Silylation of Arenes with Hydrosilane or Disilane by RhCl(CO)(PMe3)2 under Irradiation
-
Direct silylation of arenes with triethylsilane or hexamethyldisilane were catalyzed by RhCl(CO)(PMe3)2 under irradiation.
- Sakakura, Toshiyasu,Tokunaga, Yuko,Sodeyama, Touru,Tanaka, Masato
-
p. 2375 - 2378
(2007/10/02)
-