6624-02-8Relevant articles and documents
Isopropylmagnesium chloride-promoted unilateral addition of Grignard reagents to β-diketones: One-pot syntheses of β-tertiary hydroxyl ketones or 3-substituted cyclic-2-enones
Yuan, Rui,Zhao, Dan,Zhang, Li-Yuan,Pan, Xiang,Yang, Yan,Wang, Pei,Li, Hong-Feng,Da, Chao-Shan
supporting information, p. 724 - 728 (2016/01/12)
The regioselective unilateral additions of Grignard reagents to acyclic or cyclic β-diketones were effectively promoted by sub-stoichiometric amounts of i-PrMgCl to afford β-tertiary hydroxyl ketones or 3-substituted cyclic-2-enones, respectively. Also, the addition of Grignard reagents to acyclic β-diketones followed by a reaction with cyclic β-diketones in a one-pot process was put forward. The reaction mechanism was discussed in detail to explain the high regioselectivity via chemical experiments, hydrogen-deuterium exchange and mass spectrometry.
Novel photo-rearrangements of 3,3,5-triaryl-1,2-dioxolanes: Evidence for 1,5-dioxyl diradical intermediates
Kamata, Masaki,Nishikata, Yasuhiro,Kato, Mitsuaki
, p. 2407 - 2408 (2007/10/03)
3-(p-Methoxyphenyl)-substituted 1,2-dioxolanes undergo novel photo-rearrangements to afford 1,3-diaryl-3-(p-methoxyphenoxy)propan-1-ones along with 1,3,3-triaryl-3-hydroxypropan-1-ones via 1,5-dioxyl diradical intermediates.
Oxidation of Alkenes and Sulphides with a Series of Hydroperoxides having Electron-withdrawing Substituents at the α-Position
Yamamoto, Hiroshi,Miura, Masahiro,Nojima, Masatomo,Kusabayashi, Shigekazu
, p. 173 - 182 (2007/10/02)
The oxidations of alkenes and sulphides with a series of hydroperoxides, α-hydroperoxy-α-methoxyacetophenone (1), α-hydroperoxy-α,α-diphenylacetophenone (2), methyl α-hydroperoxy-α,α-diphenylacetate (3), and α-hydroperoxy-α,α-diphenylacetonitrile (4), were undertaken in a systematic fashion.The data revealed the following. (a) The reactions of electron-rich alkenes (11a and b) with hydroperoxides (1)-(4) are most likely to proceed by a mechanism similar to that with peracids, as do the oxidations of sulphides (5a-e). (b) For the reaction of less reactive alkenes (11f-k) with hydroperoxide (1) in the presence of oxygen, epoxidation by benzoylperoxyl radical contributes to a significantextent.The reaction with hydroperoxide (2) at 60 deg C also seems to proceed by a mechanism involving benzoylperoxyl radical, whereas a molecular epoxidation mechanism is important for the reaction at 30 deg C.Perhaps in accord with this, the reaction of 1,1-disubstituted ethylenes (11c-e) with hydroperoxides (1) and (2) results in the formation of considerable amounts of benzoylated products (13) and (14). (c) For the epoxidation with hydroperoxides (3) and (4), however, a molecular epoxidation process seems to predominate.The exception is the reaction of hydroperoxide (3) with (Z)-2-phenylbut-2-ene and (Z)-stilbene, having very poor reactivity, in which a peroxyl radical, produced by hydrogen abstraction from the hydroperoxide (3), plays an important role in the epoxidation.