117780-29-7Relevant articles and documents
Titanocene-Catalyzed Alkylation of Aryl-Substituted Alkenes with Alkyl Halides
Terao, Jun,Watabe, Hiroyasu,Miyamoto, Masako,Kambe, Nobuaki
, p. C-89, 2209-2214 (2003)
A new method for substitution of a vinylic hydrogen with an alkyl group (a Mizoroki-Heck type transformation) was developed by a titanocene catalyst in the presence of nBuMgCl. This reaction could proceed regio- and stereoselectively under mild conditions to afford E-olefins using primary and secondary alkyl halides. The reactions of aliphatic alkenes, e.g., 1-octene and internal alkenes, were sluggish. When t-alkyl halides were employed, alkylative dimerization of alkenes proceeded exclusively to give symmetrical vic-diarylalkanes. These reactions involved addition of alkyl radicals to arylalkenes to form benzyl radicals as a carbon-carbon bond-forming step. Dimerization of thus formed benzyl radicals afforded symmetrical alkanes and β-hydrogen elimination from benzyltitanocene intermediates gave alkylated alkenes. A possibility that titanocene activates alkenes as radical accepters was also proposed.
Electro-mediated PhotoRedox Catalysis for Selective C(sp3)–O Cleavages of Phosphinated Alcohols to Carbanions
Barham, Joshua P.,K?nig, Burkhard,Karl, Tobias A.,Reiter, Sebastian,Tian, Xianhai,Yakubov, Shahboz,de Vivie-Riedle, Regina
supporting information, p. 20817 - 20825 (2021/08/18)
We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp3)?O bonds of phosphinated alcohols to alkyl carbanions. As well as deoxygenations, olefinations are reported which are E-selective and can be made Z-selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation, and catalyst structural variations reveal that our new naphthalene monoimide-type catalyst allows for an intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity-determining C(sp3)?O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions tolerate aryl chlorides/bromides and do not give rise to Birch-type reductions.
Preparation method of inactive alkene aryl compound
-
Paragraph 0081; 0082, (2019/06/05)
The invention discloses a preparation method of an inactive alkene aryl compound. The preparation method comprises steps as follows: arylboronic acid and inactive alkene are taken as raw materials andsubjected to an oxidization Heck reaction with a mechan
Wittig Reactions of Trialkylphosphine-derived Ylides: New Directions and Applications in Organic Synthesis
McNulty, James,McLeod, David,Das, Priyabrata,Zepeda-Velázquez, Carlos
, p. 619 - 632 (2016/01/15)
The development of semi-stabilized, stabilized, and functionalized ylides derived from short-chain trialkylphosphines in the Wittig-type olefination reactions toward the synthesis of alkenes, including stilbenes, styrenes, and 1,3-dienes, as well as reagents for homologation reactions, are described. The methods allow easy access to alkenes with high (E)-stereoselectivity in good yield. These reactions are conducted with weak bases in aqueous media, which allows easy separation of water-soluble phosphine oxides. The development of a mild organocatalytic process for the Wittig reaction and extension toward the preparation of reporter stilbenes under biological conditions are also described. Applications toward the preparation of biologically active natural products and derivatives are discussed.
