61157-31-1Relevant articles and documents
Chemoselective Amide-Forming Ligation Between Acylsilanes and Hydroxylamines Under Aqueous Conditions
Deng, Xingwang,Zhou, Guan,Tian, Jing,Srinivasan, Rajavel
supporting information, p. 7024 - 7029 (2020/12/29)
We report the facile amide-forming ligation of acylsilanes with hydroxylamines (ASHA ligation) under aqueous conditions. The ligation is fast, chemoselective, mild, high-yielding and displays excellent functional-group tolerance. Late-stage modifications of an array of marketed drugs, peptides, natural products, and biologically active compounds showcase the robustness and functional-group tolerance of the reaction. The key to the success of the reaction could be the possible formation of the strong Si?O bond via a Brook-type rearrangement. Given its simplicity and efficiency, this ligation has the potential to unfold new applications in the areas of medicinal chemistry and chemical biology.
1,2-Amino Alcohols via Cr/Photoredox Dual-Catalyzed Addition of α-Amino Carbanion Equivalents to Carbonyls
Schwarz, J. Luca,Kleinmans, Roman,Paulisch, Tiffany O.,Glorius, Frank
supporting information, p. 2168 - 2174 (2020/03/03)
Herein, we report the synthesis of protected 1,2-amino alcohols starting from carbonyl compounds and α-silyl amines. The reaction is enabled by a Cr/photoredox dual catalytic system that allows the in situ generation of α-amino carbanion equivalents which act as nucleophiles. The unique nature of this reaction was demonstrated through the aminoalkylation of ketones and an acyl silane, classes of electrophiles that were previously unreactive toward addition of alkyl-Cr reagents. Overall, this reaction broadens the scope of Cr-mediated carbonyl alkylations and discloses an underexplored retrosynthetic strategy for the synthesis of 1,2-amino alcohols.
Synthesis of Acylsilanes via Catalytic Dedithioacetalization of 2-Silylated 1,3-Dithianes with 30% Hydrogen Peroxide
Kirihara, Masayuki,Suzuki, Satoshi,Ishihara, Naohiro,Yamazaki, Kento,Akiyama, Tomomi,Ishizuka, Yuki
, p. 2009 - 2014 (2017/04/26)
Acylsilanes were obtained efficiently from dedithioacetalization of 2-silylated 1,3-dithianes using 30% hydrogen peroxide catalyzed by iron(III) acetylacetonate-sodium iodide. The use of niobium(V) chloride as a catalyst instead of iron(III) acetylacetonate was also effective, except in synthesizing some acyltrimethylsilanes.
Intermolecular Schmidt reaction of alkyl azides with acyl silanes
Yu, Chun-Jiao,Li, Rui,Gu, Peiming
supporting information, p. 3568 - 3570 (2016/07/18)
The first intermolecular Schmidt reaction of alkyl azides with acyl silanes has been designed and realized, producing a range of amides with absolute site selectivity in good to excellent yields. The mechanism of the conversion has been proposed, and the reaction exhibits scope of substrates.
Brook/Elimination/Aldol Reaction (BEAR) Sequence for the Direct Preparation of Fluorinated Aldols from β,β-Difluoro-α-(trimethylsilyl)alcohols
Decostanzi, Mélanie,Van Der Lee, Arie,Campagne, Jean-Marc,Leclerc, Eric
supporting information, p. 3091 - 3097 (2015/11/03)
A methodology allowing the preparation of aldols featuring a fluorinated stereogenic center is reported. The corresponding fluoroenolates are formed in situ from stable β,β-difluoro-α-(trimethylsilyl)alcohols, through a base-mediated process involving a Brook rearrangement followed by a fluoride elimination, and are directly added to aromatic aldehydes. Two different sets of conditions were disclosed. The first one involves the stoichiometric addition of potassium tert-butoxide (t-BuOK) while the second is based on the use of a catalytic amount of an ammonium phenoxide. The latter opens the way for a catalytic and asymmetric version of this Brook/elimination/aldol reaction (BEAR) sequence.
Stereoselective syntheses of trisubstituted olefins via platinum catalysis: α-Silylenones with geometrical complementarity
Rooke, Douglas A.,Ferreira, Eric M.
supporting information; experimental part, p. 11926 - 11928 (2010/11/16)
The stereoselective syntheses of α-silylenones using catalytic PtCl2 are reported. Via alkyne activation, α- hydroxypropargylsilanes are converted to (Z)-silylenones through a highly selective silicon migration. The complementary (E)-silylenone
Evaluation of C-trialkylsilyl enol and thioenol ethers as intermediates in the synthesis of acylsilanes
Hammaecher, Catherine,Ouzzane, Imad,Portella, Charles,Bouillon, Jean-Philippe
, p. 657 - 663 (2007/10/03)
C-silyl enol ethers or thioenol ethers have been prepared by a Peterson reaction, as intermediates for acylsilane synthesis. Bis(trialkylsilyl)(methoxy) - or -(methylsulfanyl)methanes bearing identical or different trialkylsilyl groups were used as starting materials in order to assess the selectivity of the Peterson elimination step. A good selectivity was observed only with ethers bearing the TMS and TBDMS groups. However, there is no practical interest to use such reagents owing to the difficulty to obtain them in correct yields. Bis(trimethylsilyl)(methylsulfanyl)methane proved to be a good reagent for the preparation of C-silyl thioenol ethers, which are hydrolyzed under classical acid conditions to give acylsilanes in fair overall yields. This convenient procedure was extended to the synthesis of bis(acylsilanes). Graphical Abstract.
Chromium(II)-mediated synthesis of vinylbis(silanes) from aldehydes and a study of acid- and base-induced reactions of the derived epoxybis(silanes): A synthesis of acylsilanes
Hodgson, David M.,Comina, Paul J.,Drew, Michael G. B.
, p. 2279 - 2289 (2007/10/03)
The synthesis of vinylbis(silanes) 1 from aldehydes and dibromomethylenebis(trimethylsilane) using chromium(II) chloride in DMF is described. Epoxidation of vinylbis(silanes) 1 and treatment of the resulting epoxybis(silanes) 2 with sulfuric acid in metha
Vinyldisilanes as masked acylsilanes
Hodgson, David M.,Comina, Paul J.
, p. 755 - 756 (2007/10/03)
The synthesis of acylsilanes 3 from vinyldisilanes 1 by epoxidation and treatment of the resulting epoxydisilanes 2 with H2SO4 in MeOH is described.
Electroreductive synthesis of acylsilanes from acylimidazoles
Kise, Naoki,Kaneko, Hiroaki,Uemoto, Norihisa,Yoshida, Jun-Ichi
, p. 8839 - 8842 (2007/10/02)
Electroreduction of acylimidazoles in the presence of chlorotrimethylsilane gave the corresponding acylsilanes in satisfactory yields. Acylsilanes having a functional group such as an alkoxycarbonyl or chloro group also were synthesized effectively.
