4131-43-5Relevant academic research and scientific papers
The Acetate Proton Shuttle between Mutually Trans Ligands
De Aguirre, Adiran,Díez-González, Silvia,Maseras, Feliu,Martín, Marta,Sola, Eduardo
, p. 2645 - 2651 (2018)
This work addresses a counterintuitive observation in the reactivity of the well-known ruthenium complexes [Ru(X)H(CO)(PiPr3)2], according to which the 5-coordinate chloro complex (X = Cl, 1) is less reactive toward phenylacetylene than its 6-coordinate acetate analogue (X = O2-OC(O)Me, 3), since 3 undergoes a hydride-to-alkenyl-to-alkynyl transformation, whereas the reaction of 1 stops at the alkenyl derivative. The experimental kinetics of the key alkenyl-to-alkynyl step in the acetate complex are compared to the results of DFT calculations, which disclose the ability of the acetate not only to assist the alkyne C-H activation step via a CMD mechanism but also to subsequently deliver the proton to the alkenyl ligand. Possible consequences of this mechanistic resource connecting mutually trans ligands are briefly discussed on the basis of reported chemoselectivity changes induced by carboxylate ligands in 1-alkyne hydrosilylations catalyzed by this type of ruthenium complexes.
Catalytic Decarboxylation of Silyl Alkynoates to Alkynylsilanes
Aoyagi, Keiya,Choi, Jun-Chul,Kawatsu, Takahiro,Matsumoto, Kazuhiro,Nakajima, Yumiko,Sato, Kazuhiko
supporting information, (2020/09/15)
Herein, we describe a decarboxylative approach to the preparation of alkynylsilanes. Treatment of a silyl alkynoate in N,N-dimethylformamide (DMF) at 80 °C in the presence of catalytic amounts of CuCl and PCy3 produced the corresponding alkynylsilane in excellent yield. The copper-catalyzed decarboxylation proceeded smoothly with low catalyst loadings (0.5 mol % of CuCl and 1.0 mol % of PCy3) under mild reaction conditions and is easily scalable to gram quantities.
Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes
Huang, Pan,Xu, Dawen,Reich, Robert M.,Kaiser, Felix,Liu, Boping,Kühn, Fritz E.
supporting information, p. 1574 - 1577 (2019/05/17)
A first example of an Et2Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.
Silicon(II) Cation Cp*Si:+ X-: A New Class of Efficient Catalysts in Organosilicon Chemistry
Fritz-Langhals, Elke
, p. 2369 - 2377 (2019/10/28)
The catalytic activity of the pentamethylcyclopentadienylsilicon(II) cation Cp*Si:+ was investigated. It was shown that Cp*Si:+ efficiently catalyzes reactions of technical relevance in organosilicon chemistry: Cp*Si:+ proved to be a very efficient nonmetallic catalyst for the hydrosilylation of olefins at low catalyst amounts of 0.01 mol % and for the Piers-Rubinsztajn reaction in order to make controlled silicone topologies. The thermal induction of hydrosilylation which is important for the manufacturing of silicone rubber can be achieved by small amounts of alkoxysilanes.
Nickel-Catalyzed Decarboxylative C–Si Bond Formation: A Regioselective Cross-Coupling Between Trialkyl Silanes and α,β-Unsaturated Carboxylic Acids
Allam, Bharat Kumar,Azeez, Sadaf,Kandasamy, Jeyakumar
, (2019/08/26)
This report presents the first example of nickel-catalyzed mild decarboxylative cross-coupling reaction for the regioselective formation of C–Si bond. An easily accessible and significantly stable Ni (dmg)2 owes the role of key promoter. This r
Tuning the Selectivity of AuPd Nanoalloys towards Selective Dehydrogenative Alkyne Silylation
Wissing, Maren,Studer, Armido
supporting information, p. 5870 - 5874 (2019/03/21)
The cross-dehydrogenative coupling of terminal alkynes and hydrosilanes catalyzed by AuPd nanoalloys is described. Metal nanoparticles are readily prepared in 15 minutes from commercially available and cheap starting materials by using a photochemical app
Role of C, S, Se and P donor ligands in copper(i) mediated C-N and C-Si bond formation reactions
Srinivas, Katam,Prabusankar, Ganesan
, p. 32269 - 32282 (2018/09/29)
The first comparative study of C, S, Se and P donor ligands-supported copper(i) complexes for C-N and C-Si bond formation reactions are described. The syntheses and characterization of eight mononuclear copper(i) chalcogenone complexes, two polynuclear co
A novel synthesis of polysubstituted chromenes from various salicylaldehydes and alkynes under mild conditions
Tanaka, Kenta,Hoshino, Yujiro,Honda, Kiyoshi
supporting information, p. 2448 - 2450 (2016/05/19)
A novel synthesis of poly substituted chromenes from various salicylaldehydes and alkynes not having electron withdrawing substituents under mild conditions has been developed. The procedure is applicable for easily available various substituted salicylal
Rapid synthesis of crowded aromatic architectures from silyl acetylenes
Hein, Samuel J.,Arslan, Hasan,Keresztes, Ivan,Dichtel, William R.
supporting information, p. 4416 - 4419 (2015/01/08)
Congested aromatic systems were prepared by benzannulating silyl-protected arylacetylenes. The silyl groups may be retained in the naphthalene products and transformed into iodides in high yield. The desirable attributes of this strategy, particularly its remarkable tolerance of sterically hindered alkynes, are showcased in the efficient synthesis of a congested, branched oligo(naphthalene). As such, benzannulations of diaryl and silyl-protected acetylenes show outstanding promise for accessing new aromatic architectures.
Iridium-promoted conversion of chlorosilanes to alkynyl derivatives in a one-pot reaction sequence
Kownacki, Ireneusz,Orwat, Bartosz,Marciniec, Bogdan
, p. 3051 - 3059 (2014/07/08)
By making use of the catalytic potential of the iridium system [{Ir(μ-Cl)(CO)2}2]/NEt(i-Pr)2 in the synthesis of silyl-functionalized alkynes via silylative coupling of terminal alkynes/diynes with iodosilanes, we propose
