(Diisopropoxymethylsilyl)methyl Grignard reagent: a new, practically useful nucleophilic hydroxymethylating agent

Abstract

10"6 and 1.4 X 10-4 M. None of these runs gave good first-order or second-order plots, and we therefore obtained the order of the reaction in naphthalene by analyzing the initial rates ( ) as shown in Figure 2. By this method the order in napthalene was determined to be 1.5. This surprising result was verified by reexamination of the full kinetic runs, which were found to fit plots for a reaction 1.5 order in naphthalene. These results are in contrast to those of Ridd and Co-workers,4 who found N(EI)-catalyzed nitration of N^V-dimethylaniline to be first order in the aromatic. This finding is moreover obviously not in accord (7)

[cyclo-CH2{Sn(Cl2)CH2Si(Me2)}2O]: Synthesis and Complexation Behaviour of a Novel, Cyclic, Bidentate Lewis Acid and Its Conversion into a Tin-Containing Fluorosilane with Intermolecular Si−F⋅⋅⋅Sn Bridges

“…Synthesis and properties of [ cyclo ‐CH 2 {Sn(Cl 2 )CH 2 Si(Me 2 )} 2 O] (2) : The reaction of bis(diphenylfluorostannyl)methane27 with two molar equivalents of Me 2 ( i PrO)SiCH 2 MgCl57 afforded bis{[(dimethylisopropoxysilyl)methyl]diphenylstannyl}methane ( 1 ) as a colourless oil in almost quantitative yield (Scheme ).…”

Cross‐Coupling Reaction of Alkenyl Sulfoximines and Alkenyl Aminosulfoxonium Salts with Organozincs by Dual Nickel Catalysis and Lewis Acid Promotion

“…[33] However,d espite severala ttempts aN i-catalyzed CCR of (E,R)-2 with 19/MgBrCl could not be achieved. [34] Treatment of (E,R)-2 of 99.5:0.5 d.r.w ith 21 (2 equiv), Ni(dppp)Cl 2 (20 mol %), and MgBr 2 /Et 2 Oa fforded the allylic silane (E)-3d in 92 %y ield and 98.5:1.5 d.r.T he configurationo f the alkenew as clarified by NOE experiments. [35] Organozinc 21 is structurally remarkable because in the crystal the Zn atom is coordinated by the two Ca toms and the Oa tom of as econd molecule in at rigonal planar fashion.…”

“…[33] However,d espite severala ttempts aN i-catalyzed CCR of (E,R)-2 with 19/MgBrCl could not be achieved. As an alternative, as tepwise introduction of the hydroxymethyl group of (E)-3e was envisioned, [34] by using bis(alkoxysilylmethyl)-zinc 21,w hich was synthesized salt-freef rom Grignard reagent 20 and ZnCl 2 . [35] Organozinc 21 is structurally remarkable because in the crystal the Zn atom is coordinated by the two Ca toms and the Oa tom of as econd molecule in at rigonal planar fashion.…”

“…[35] It was to be expected that the alkoxy-substituted allylic silane (E)-3d can be oxidized to the allylic alcohol (E)-3e. [34] Treatment of (E,R)-2 of 99.5:0.5 d.r.w ith 21 (2 equiv), Ni(dppp)Cl 2 (20 mol %), and MgBr 2 /Et 2 Oa fforded the allylic silane (E)-3d in 92 %y ield and 98.5:1.5 d.r.T he configurationo f the alkenew as clarified by NOE experiments. As imilar CCR of the isomeric alkenyls ulfoximine (Z,S)-2 of 96.4:3.6 d.r.…”

Unsaturated Sugars: A Rich Platform for Methodological and Synthetic Studies

“…Radical cyclization of the latter under Stork's conditions [110c] in the presence of an excess of acrylonitrile gave 166. Oxidative work-up as described by Tamao [115] and subsequent acetylation gave the triacetate 167, in which the desired C-1 and C-2 carbon branches had been installed.…”