10519-88-7Relevant articles and documents
Zinc mediated allylations of chlorosilanes promoted by ultrasound: Synthesis of novel constrained sila amino acids
Ramesh, Remya,Reddy, D. Srinivasa
supporting information, p. 4093 - 4097 (2014/06/10)
A simple, fast and efficient method for allylation and propargylation of chlorosilanes through zinc mediation and ultrasound promotion is reported. As a direct application of the resulting bis-allylsilanes, three novel, constrained sila amino acids are prepared for the first time. The design and synthesis of the constrained sila analogue of GABA (γ-amino butyric acid) is a highlight of this work. This journal is the Partner Organisations 2014.
Selective mono- and di-allylation and allenylation of chlorosilanes using indium
Li, Zhifang,Yang, Chenjun,Zheng, Hongfang,Qiu, Huayu,Lai, Guoqiao
scheme or table, p. 3771 - 3779 (2009/02/08)
Allyl and allenyl groups have been introduced into silicon systems by the allylation and allenylation of chlorosilanes using allyl bromide or propargyl bromide with indium. The allylation of chlorosilanes afforded a variety of aryl, aralkyl, and alkenyl substituted allylsilanes. By applying this method, the reactions of 1-bromo-3-methylbut-2-ene, 3-bromo-2-methylprop-1-ene and 3-bromobut-1-ene with chlorosilanes also proceed smoothly to give regioselectively allylic rearrangement products in good yields. Mediated by indium, dichlorosilanes (R2SiCl2) and trichlorosilanes (RSiCl3) can either afford monoallylated silanes or diallylated silanes depending on the amount of allyl bromide and indium used.
Controlled introduction of allylic group to chlorosilanes
Li, Zhifang,Cao, Xiaojun,Lai, Guoqiao,Liu, Jinhua,Ni, Yong,Wu, Jirong,Qiu, Huayu
, p. 4740 - 4746 (2007/10/03)
Allylation of chlorosilanes has been achieved with allylsamarium bromide, especially in a controlled manner. Thus allylation of trisubstituted chlorosilanes (R3SiCl) afforded a variety of aryl, aralkyl, and alkenyl substituted allylsilanes. Dichlorosilanes (R2SiCl2) can either afford monoallylated silanes or diallylated silanes depending on the amount of allylsamarium bromide used. Similarly, trichlorosilanes (RSiCl3) can selectively afford mono-, di-, and tri-allylation products. Finally, perchlorosilane (SiCl4) was allylated stepwise and the corresponding silanes containing one, two, three or four allylic groups, respectively, were obtained in satisfactory yields.
Medium-dependent lithiated side products in the reductive lithiation of allylic phenyl thioethers. Diethyl ether versus tetrahydrofuran
Screttas, Constantinos G.,Heropoulos, Georgios A.,Micha-Screttas, Maria,Steele, Barry R.
, p. 4357 - 4360 (2007/10/03)
Diethyl ether is a convenient solvent for the reductive lithiation of allylic phenyl thioethers without the serious complications, which occur when the reaction is carried out in tetrahydrofuran.
Cross-coupling of triallyl(aryl)silanes with aryl bromides and chlorides: An alternative convenient biaryl synthesis
Sahoo, Akhila K.,Oda, Takuro,Nakao, Yoshiaki,Hiyama, Tamejiro
, p. 1715 - 1727 (2007/10/03)
Cross-coupling of a diverse range of aryl bromides with triallyl(aryl)silanes is effective in the presence of PdCl2/PCy 3 and tetrabutylammonium fluoride (TBAF) in DMSO-H2O to give various biaryls in good yields. It is worthwhile to note that the all-carbon-substituted arylsilanes, stable towards moisture, acid, and base and easily accessible, serve as a highly practical alternative to their aryl(halo)silane counterparts. A catalyst system consisting of [η3-C3H5)PdCl]2 and 2-[2,4,6-(i-Pr)3C6Ha]-C6H4PCy 2 and use of TBAF· 3 H2O in THF-H2O are effective especially for the cross-coupling with aryl chlorides. Both of the catalyst systems tolerate a broad spectrum of common functional groups. The high efficiency of reactions is presumably due to the ready cleavage of the allyl groups upon treatment with TBAF·3 H2O and an appropriate amount of water. Diallyl(diphenyl)silane also cross-couples with various aryl bromides and chlorides in good yields, whereas allyl(triphenyl)silane gives the cross-coupled products in only moderate yields. Through sequential cross-coupling of bromochlorobenzenes with different arylsilanes, a range of unsymmetrical terphenyls are accessible in good overall yields.
Stereoselective polycyclisations of allyl and enyne silanes: Evidence for bicyclo[3.2.0]hept-1(7)ene structure
Oba, Gabriel,Moreira, Georges,Manuel, Georges,Koenig, Max
, p. 324 - 330 (2007/10/03)
The intramolecular copper(I)-catalyzed [2 + 2]-photocycloaddition of diphenyldiallysilane (1) (or tetraallylsilane (4)) led to sila-3-bicyclo[3.2.0]heptane (3) (or to spiro analogous 6) in the cis (or cis-cis) configuration whereas the α,ω-diiodide (2) obtained by cyclozirconation of 1 (or from the homologous tetraiodide 5) followed by addition of n-BuLi, produced the sila-3-bicyclo[3.2.0]heptane (3) (or to the spiro analogous 6) in the trans (or trans-trans configuration). The same cyclozirconation reaction, starting from the hetero enyne 7, selectively led to the highly strained silacyclobutene moiety 15 which represents the first stable hetero bicyclo[3.2.0]hept-1(7)ene skeleton, hypothetical intermediate in methathesis reactions.
Proton Addition to Silylstyrenes: Overcoming the Predilection for Protiodesilylation
Henry, Courtney,Brook, Michael A.
, p. 11379 - 11390 (2007/10/02)
Normally, organosilyl nucleophiles such as vinylsilanes and allylsilanes undergo protiodesilylation reactions with protons.To favour addition reactions under these conditions, the ligands on silicon have been modified such that the leaving group ability and, simultaneously, the β-effect of the silyl group is reduced.In the case of allylsilanes, the use of dichlorosilyl groups does not significantly favour addition over substitution processes at the olefin.However, with vinylsilanes bearing a second ?-nucleophile, a dichlorosilyl group can be used to regioselectively direct the formation of two bonds (C-H and C-C) sequentially in a process in which the silicon is not lost from the molecule, but may ultimately be cleaved leading to the formation of diols.Thus, benzyldichlorostyrylsilane 7, after cyclization to 9 in the presence of triflic acid, is converted into diol 12.The synthetic utility of this process is restricted by the relatively low reactivity of the styryl ?-system and the necessarily reactive electrophiles needed to initiate the process.The effect of changing from electron-donating groups to electronegative groups on silicon on reaction mechanism is discussed.
