77644-39-4Relevant academic research and scientific papers
Utilization of a Trimethylsilyl Group as a Synthetic Equivalent of a Hydroxyl Group via Chemoselective C(sp3)-H Borylation at the Methyl Group on Silicon
Torigoe, Takeru,Ohmura, Toshimichi,Suginome, Michinori
, p. 2943 - 2956 (2017/03/23)
A conversion of trimethylsilylalkanes into the corresponding alcohols is established based on an iridium-catalyzed, chemoselective C(sp3)-H borylation of the methyl group on silicon. The (borylmethyl)silyl group formed by C(sp3)-H borylation is treated with H2O2/NaOH, and the resulting (hydroxymethyl)silyl group is converted into a hydroxyl group by Brook rearrangement, followed by oxidation of the resulting methoxysilyl group under Tamao conditions. An alternative route proceeding through the formylsilyl group formed from a (hydroxymethyl)silyl group by Swern oxidation is also established. The method is applicable to substituted trimethylsilylcycloalkanes and 1,1-dimethyl-1-silacyclopentane for conversion into the corresponding stereodefined cycloalkyl alcohols and 1,4-butanediol.
Selectivity in Organic Group Transfer in Reactions of Mixed Diorganomanganese(II) and Triorganomanganate(II) with 2-Cyclohexen-1-one or Cyclohexanecarbaldehyde
Yorimitsu, Hideki,Hayashi, Yasuhiro,Tang, Jun,Shinokubo, Hiroshi,Oshima, Koichiro
, p. 2297 - 2300 (2007/10/03)
The unsymmetrical diorganomanganeses(II) (R1R2Mn) and magnesium triorganomanganates(II) (R21R2MnMgX) reacted with 2-cyclohexen-1-one to produce the 1,4-addition products in moderate to good yields. The approximate reactivity order obtained from the product distribution was CH2=CHCH2 > PhS > n-Bu > Ph > Me, Me3SiCH2, n-C6H13-CΞC. In contrast, the reactivity order for the addition of these reagents to cyclohexanecarbaldehyde was CH2=CHCH2 > Ph > Me > n-Bu > n-C6H13CΞC > Me3SiCH2.
Organocuprates as Electron Transfer Reagents. Evaluation for Conjugate Addition of Electrophiles to α,β-Unsaturated Ketones
Hannah, Donald J.,Smith, Robin A.J.,Teoh, Irene,Weavers, Rex T.
, p. 181 - 188 (2007/10/02)
The reaction of a series of organocuprate containing alkyl, aryl, alkynyl, silylalkyl or phenylthio groups with (1) is reported.Some of these organocuprates showed electron transfer properties and were unreactive toward conjugate addition, hence have pote
ADDITION OF TRIMETHYLSILYLMETHYLMAGNESIUM CHLORIDE TO α,β-UNSATURATED CARBONYLS
Taylor, Richard T.,Galloway, James G.
, p. 295 - 300 (2007/10/02)
Reactions of α,β-unsaturated carbonyl compounds with Me3SiCH2MgCl, prepared from chloromethyltrimethylsilane , were examined.Unlike its lithium counterpart (Me3SiCH2Li), which adds to α,β-unsaturated ketones in the 1,2-sense, the Grignard reagent afforts γ silanes via a 1,4-addition sequence.This tendency is accenturated by the addition of Cu2Br2.Addition of the Grignard reagent to α,β-unsaturated aldehydes gives the simple 1,2-addition products.
