40493-34-3Relevant academic research and scientific papers
A new entry of highly selective and nucleophilic BrH2C-and CLH2c-titanium complexes for carbonyl coupling
Yan, Tu Hsin,Ananthan, Bakthavachalam,Chang, Su Haur
, p. 778 - 787 (2019)
The direct coupling of various aldehydes and ketones with CH2Br2 or CH2Cl2 promoted by TiCl4-Mg bimetallic complex provides an extremely simple, practical, and efficient approach for the construction of bromomethyl or chloromethyl carbinols. The high chemoselectivity of this chemistry is illus-trated by the TiCl4-Mg-promoted selective coupling of CH2Br2 or CH2Cl2 with an aldehyde in the presence of ketone and selective transfer of CH2Br or CH2Cl to saturated carbonyl moiety. This protocol is also suitable for sterically hindered and enoliza-ble carbonyl compounds.
Difunctionalization of Alkenes Using 1-Chloro-1,2-benziodoxol-3-(1H)-one
Egami, Hiromichi,Yoneda, Takahiro,Uku, Minako,Ide, Takafumi,Kawato, Yuji,Hamashima, Yoshitaka
, p. 4020 - 4030 (2016/06/09)
Difunctionalization of alkenes with 1-chloro-1,2-benziodoxol-3-(1H)-one (1) was investigated. Various additional nucleophiles were tested, and oxychlorination, dichlorination, azidochlorination, chlorothiocyanation, and iodoesterfication were demonstrated. The oxychlorination product was obtained efficiently when the reaction was operated in water. Dichlorination occurred in the presence of a Lewis basic promoter, such as 4-phenylpyridine N-oxide, as an additive. The reaction with in situ-generated azido anion afforded azidochlorinated compounds with a chlorine atom at the terminal position, while the reaction with trimethylsilyl isothiocyanate produced chlorothiocyanation adducts with a chlorine atom at the benzylic position. On the other hand, when 1 was treated with tetra-n-butylammonium iodide prior to the addition of alkenes, only iodoesterification occurred selectively. These mild reactions enable convenient site-selective difunctionalizations of substrates having two alkene moieties. NMR experiments suggested that the electrophilic reactive species in each reaction varied depending on the nature of the added nucleophile.
