89567-75-9Relevant articles and documents
A Bench-Stable, Single-Component Precatalyst for Silyl-Heck Reactions
Krause, Sarah B.,McAtee, Jesse R.,Yap, Glenn P. A.,Watson, Donald A.
, p. 5641 - 5644 (2017)
Studies of the silyl-Heck reaction aimed at identifying active palladium complexes have revealed a new species that is formed in situ. This complex has been identified as the palladium iodide dimer, [(JessePhos)PdI2]2, which has been
Visible-Light Photoredox-Catalyzed α-Regioselective Conjugate Addition of Allyl Groups to Activated Alkenes
Gontala, Arjun,Woo, Sang Kook
supporting information, p. 3223 - 3228 (2020/07/06)
The α-regioselective conjugate addition of allyl groups to activated alkenes is a poorly explored area of research. Herein, we report an α-adduct and (E)-isomer selective conjugate addition of allylsilanes to activated alkenes by visible-light photoredox catalysis. The reaction involves allylic radicals that can be generated from allylsilanes through a photoinduced single-electron transfer mechanism. (Figure presented.).
Rational design of a second generation catalyst for preparation of allylsilanes using the silyl-Heck reaction
McAtee, Jesse R.,Yap, Glenn P. A.,Watson, Donald A.
supporting information, p. 10166 - 10172 (2014/08/05)
Using rational ligand design, we have developed of a second-generation ligand, bis(3,5-di-tert-butylphenyl)(tert-butyl)phosphine, for the preparation of allylsilanes using the palladium-catalyzed silyl-Heck reaction. This new ligand provides nearly complete suppression of starting material alkene isomerization that was observed with our first-generation catalyst, providing vastly improved yields of allylsilanes from simple alkene starting materials. The studies quantifying the electronic and steric properties of the new ligand are described. Finally, we report an X-ray crystal structure of a palladium complex resulting from the oxidative addition of Me3SiI using an analogous ligand that provides significant insight into the nature of the catalytic system.
Preparation of allyl and vinyl silanes by the palladium-catalyzed silylation of terminal olefins: A silyl-heck reaction
McAtee, Jesse R.,Martin, Sara E. S.,Ahneman, Derek T.,Johnson, Keywan A.,Watson, Donald A.
supporting information; experimental part, p. 3663 - 3667 (2012/05/20)
Installing silicon is easy! A high-yielding protocol for the palladium-catalyzed silylation of terminal alkenes is reported. This method allows facile conversion of styrenes to E-β-silyl styrenes by using iodotrimethylsilane (TMSI) or chlorotrimethylsilane/lithium iodide (see scheme). Terminal allyl silanes with good E/Z ratios are also readily accessed from α-olefins.
Synthesis of allylsilanes by reductive lithiation of thioethers
Streiff, Stephane,Ribeiro, Nigel,Desaubry, Laurent
, p. 7592 - 7598 (2007/10/03)
Although much work in reductive lithiation has been done, the utilization of allylthioethers bearing various substituents to prepare allylsilanes has not been explored. The main reason clearly stems from the anticipated lack of regioselectivity. We describe herein the first study on the regioselectivity of the reductive silylation involving dissymmetric allylthioethers. We surveyed a broad spectrum of parameters and showed that this process displays a great dependence of the reaction conditions. We also discovered that an electron transporter, DBB or naphthalene, can cleave THF at room temperature by sonication, to generate a strong base, 4-lithiobutoxide. This feature was successfully exploited to the straightforward synthesis of bis-silanes in one pot. Examples are provided for maximizing both the chemical yield and the regioselectivity of the reductive silylation through the tuning of the reaction conditions. By changing these conditions, several allylsilanes can be selectively synthesized from one thioether.
Facial-selective allylation of methyl ketones for the asymmetric synthesis of α-substituted tertiary homoallylic ethers
Tietze, Lutz F.,Voelkel, Ludwig,Wulff, Christian,Weigand, Berthold,Bittner, Christian,McGrath, Paul,Johnson, Keyji,Schaefer, Martina
, p. 1304 - 1308 (2007/10/03)
The asymmetric synthesis of enantiomerically pure α-substituted tertiary homoallylic ethers 4a, 11 and 12a-c by the allylation of ethyl methyl ketone (1a) with γ-substituted allylsilanes 9 a-h is described. The allylsilanes were obtained by a nickel-catal
1,4-Carbosilylation of 1,3-dienes via palladium catalyzed three-component coupling reaction
Obora, Yasushi,Tsuji, Yasushi,Kawamura, Takashi
, p. 9814 - 9821 (2007/10/03)
Three-component coupling reaction of acid chlorides, organodisilanes, and 1,3-dienes achieves 1,4-carbosilylation of the 1,3-dienes to afford allylic silanes as the product. Bis(dibenzylideneacetone)palladium, a naked Pd(0) complex without donating ligand
COMPLEXES OF TRANSITION METALS IN THE CHEMISTRY OF CONJUGATED SYSTEMS. III. REACTION OF DIENE HYDROCARBONS WITH ORGANOMAGNESIUM COMPOUNDS IN THE PRESENCE OF SALTS AND COMPLEXES OF TRANSITION METALS
Zubritskii, L. M.,Romashchenkova, N. D.,Petrov, A. A.
, p. 2157 - 2167 (2007/10/02)
The effect of the structure of the reagents and the nature of the catalyst on the direction and selectivity in the reaction of 1,3-dienes and their derivatives with aromatic Grignard reagents was investigated.It was shown that in the presence of salts and complexes of iron(III) 1,3-alkadienes R1CH=C(R2)C(R3)=CH2 react with arylmagnesium halides to form trans-(E)-1-aryl-1,3-alkadienes, whereas the sterically hindered (R2, R3=CH3) cyclic 1,3-alkadienes and also 1,2-alkadienes give mainly adducts (1:1).Catalysis by the phosphine complexes of nickel(II) leads to the formation of telomeric (2:1) (E)-1-aryl-2,7- and (E,E)-1-aryl-2,6-alkadienes.The results demonstrate the determining role of the stereochemical conditions for the coordination of the diene in the course of the reaction and also the significant contribution from the processes of one-electron reduction of the catalyst.
