1726-14-3Relevant articles and documents
Lewis acid-catalyzed ring-opening reactions of methylenecyclopropanes with alcoholic or acidic nucleophiles
Shi, Min,Xu, Bo
, p. 2145 - 2148 (2002)
(matrix presented) Nu-H can be alcohols, thiols, phenols, carboxylic acids yield: 60%-100%. Methylenecyclopropanes can react with various nucleophiles such as alcohols, phenols, carboxylic acids, and thiols to give the corresponding homoallylic esters or
Early main group metal catalysis: How important is the metal?
Harder, Sjoerd,Penafiel, Johanne,Maron, Laurent
, p. 201 - 206 (2015)
Organocalcium compounds have been reported as efficient catalysts for various alkene transformations. In contrast to transition metal catalysis, the alkenes are not activated by metal-alkene orbital interactions. Instead it is proposed that alkene activation proceeds through an electrostatic interaction with a Lewis acidic Ca2+. The role of the metal was evaluated by a study using the metal-free catalysts: [Ph2N-Me4N+] and [Ph3C-][Me4N- ]. These "naked" amides and carbanions can act as catalysts in the conversion of activated double bonds (C=O and C=N) in the hydroamination of Ar-N=C=O and R-N=C=N=R (R=alkyl) by Ph2NH. For the intramolecular hydroamination of unactivated C=C bonds in H2C=CHCH2CPh2CH2NH2 the presence of a metal cation is crucial. A new type of hybrid catalyst consisting of a strong organic Schwesinger base and a simple metal salt can act as catalyst for the intramolecular alkene hydroamination. The influence of the cation in catalysis is further evaluated by a DFT study.
Iron-Catalyzed Radical Cleavage/C?C Bond Formation of Acetal-Derived Alkylsilyl Peroxides
Shiozaki, Yoko,Sakurai, Shunya,Sakamoto, Ryu,Matsumoto, Akira,Maruoka, Keiji
supporting information, p. 573 - 576 (2020/02/20)
A novel radical-based approach for the iron-catalyzed selective cleavage of acetal-derived alkylsilyl peroxides, followed by the formation of a carbon–carbon bond is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the acetal moiety and the carbon electrophile. Mechanistic studies suggest that the present reaction proceeds through a free-radical process involving carbon radicals generated by the homolytic cleavage of a carbon–carbon bond within the acetal moiety. A synthetic application of this method to sugar-derived alkylsilyl peroxides is also described.
Conversion of Carbonyl Compounds to Olefins via Enolate Intermediate
Cao, Zhi-Chao,Xu, Pei-Lin,Luo, Qin-Yu,Li, Xiao-Lei,Yu, Da-Gang,Fang, Huayi,Shi, Zhang-Jie
supporting information, p. 781 - 785 (2019/06/24)
A general and efficient protocol to synthesize substituted olefins from carbonyl compounds via nickel catalyzed C—O activation of enolates was developed. Besides ketones, aldehydes were also suitable substrates for the presented catalytic system to produce di- or tri- substituted olefins. It is worth noting that this approach exhibited good tolerance to highly reactive tertiary alcohols, which could not survive in other reported routes for converting carbonyl compounds to olefins. This method also showed good regio- and stereo-selectivity for olefin products. Preliminary mechanistic studies indicated that the reaction was accomplished through nickel catalyzed C—O activation of enolates, thus offering helpful contribution to current enol chemistry.
Palladium-Catalyzed C?H Alkenylation of Arenes with Alkynes: Stereoselective Synthesis of Vinyl Chlorides via a 1,4-Chlorine Migration
Li, Zhen,Duan, Wei-Liang
supporting information, p. 16041 - 16045 (2018/11/23)
A directing group-free, ligand-promoted palladium-catalyzed C?H arylation of internal alkynes with simple arenes was developed. Alkenyl chlorides resulting from a 1,4-chlorine migration or trisubstituted alkenes were produced in moderate to good yields depending on the type of alkyne.