35286-92-1Relevant articles and documents
Selenenate Anions (PhSeO?) as Organocatalyst: Synthesis of trans-Stilbenes and a PPV Derivative
Zheng, Zhipeng,Trofymchuk, Oleksandra S.,Kurogi, Takashi,Varela, Elena,Mindiola, Daniel J.,Walsh, Patrick J.
supporting information, p. 659 - 666 (2020/01/02)
The selenenate anion (RSeO?) is introduced as an active organocatalyst for the dehydrohalogen coupling of benzyl halides to form trans-stilbenes. It is shown that RSeO? is a more reactive catalyst than the previously reported sulfur analogues (sulfenate anion, RSO?) and selenolate anions (RSe?) in the aforementioned reaction. This catalytic system was also applied to the benzylic-chloromethyl-coupling polymerization (BCCP) of a bis-chloromethyl arene to form ppv (poly(p-phenylene vinylene))-type polymers with high yields, Mn (average molecular weight) up to 13,000 and ? (dispersity) of 1.15. (Figure presented.).
Catalytic Transfer Hydrogenation Using Biomass as Hydrogen Source
Antonchick, Andrey P.,Manna, Srimanta
, p. 3094 - 3098 (2018/09/14)
We developed an operationally simple method for the direct use of biomass-derived chemical entities in a fundamentally important process, such as hydrogenation. Various carbohydrates, starch, and lignin were used for stereoselective hydrogenation. Employing a transition metal catalyst and a novel catalytic system, the reduction of alkynes, alkenes, and carbonyl groups with high yields was demonstrated. The regioselective hydrogenation to access different stereoisomers was established by simple variations in the reaction conditions. This work is based on an unprecedented catalytic system and represents a straightforward application of biomass as a reducing reagent in chemical reactions.
A Novel Catalyst-Free Synthesis of 2,2-Diaryl Enamides from Stilbenes via a Nitrene Transfer Reaction
Zhang, Yuanyuan,Ye, Wenjing,Zhang, Hui,Xiao, Xiao
supporting information, p. 5720 - 5724 (2019/08/26)
A novel catalyst-free nitrene transfer reaction between stilbenes and iminoiodinanes was achieved for the first time, which provides an efficient and environmentally friendly way to access variously substituted 2,2-diaryl enamides under mild conditions. Mechanistic investigations suggested the reaction proceed via nitrene transfer and aromatic rearrangement with iminoiodinane also acting as a Lewis acid, benefitting the ring-opening of the aziridine intermediate.
Selenolate Anion as an Organocatalyst: Reactions and Mechanistic Studies
Trofymchuk, Oleksandra S.,Zheng, Zhipeng,Kurogi, Takashi,Mindiola, Daniel J.,Walsh, Patrick J.
, p. 1685 - 1692 (2018/03/21)
A new organocatalyst, the selenolate anion [RSe]–, generated from bench-stable and commercially available diphenyl diselenide or from phenyl benzyl selenide (10 mol%) is introduced. Benchmarking is performed in the conversion of benzylic chlorides into trans-stilbenes selectively at room temperature. Mechanistic studies support the intermediacy of the selenolate anion and of 1,2-diphenylethyl phenyl selenide. (Figure presented.).
A new role for sulfenate anions: Organocatalysis
Schwan, Adrian L.
, p. 226 - 227 (2015/03/03)
(Chemical Equation Presented) The sulfenate anion is introduced for the first time as a catalyst and was found to facilitate the conversion of benzyl halides to trans-stilbenes. CPME=Cyclopentyl methyl ether.
Tert-butyl phenyl sulfoxide: A traceless sulfenate anion precatalyst
Zhang, Mengnan,Jia, Tiezheng,Sagamanova, Irina K.,Pericás, Miquel A.,Walsh, Patrick J.
supporting information, p. 1164 - 1167 (2015/03/14)
tert-Butyl phenyl sulfoxide is employed as a traceless precatalyst for the generation of sulfenate anions under basic conditions and has been used to catalyze the coupling of benzyl halides to trans-stilbenes. The advantage of this precatalyst over previous precatalysts is that the byproduct generated on catalyst formation is a gas, facilitating product isolation in high purity. Using this second generation catalyst, a variety of trans-stilbenes were generated in 39-98% isolated yield.
A new class of organocatalysts: Sulfenate anions
Zhang, Mengnan,Jia, Tiezheng,Yin, Haolin,Carroll, Patrick J.,Schelter, Eric J.,Walsh, Patrick J.
supporting information, p. 10755 - 10758 (2015/05/13)
Sulfenate anions are known to act as highly reactive species in the organic arena. Now they premiere as organocatalysts. Proof of concept is offered by the sulfoxide/sulfenate-catalyzed (1-10 mol%) coupling of benzyl halides in the presence of base to generate trans-stilbenes in good to excellent yields (up to 99%). Mechanistic studies support the intermediacy of sulfenate anions, and the deprotonated sulfoxide was determined to be the resting state of the catalyst. Sulfenates take center stage: Sulfenate anions are known as highly reactive species in the organic arena. Now they premiere as organocatalysts: A sulfoxide/sulfenate (1-10 mol%) promotes the transformation of benzyl halides into trans-stilbenes under basic conditions (up to 99% yield). CPME=cyclopentyl methyl ether.
Rhodium-catalyzed cross-coupling of alkenyl halides with arylboron compounds
Matsuda, Takanori,Suzuki, Kentaro,Miura, Norio
supporting information, p. 3396 - 3400 (2013/12/04)
The rhodium(I)-catalyzed reaction between arylboronic esters and excess 1,2-dichloroethene selectively afforded (2-chlorovinyl)arenes. Double arylation yielding 1,2-diarylethenes was observed when 1,2-dibromoethene was reacted with 2.5 equivalents of aryl
Transition metal-free domino sequential synthesis of (E)-stilbenes, biaryl methanes and biaryl ethers using Et2AlCl as a Lewis acid
Sarkar, Satinath,Jana, Manoranjan,Tadigoppula, Narender
, p. 18755 - 18758 (2013/10/22)
A transition metal-free domino process has been developed, for the first time, to synthesize (E)-stilbenes, biaryl methanes and biaryl ethers from substituted α,β-unsaturated ketones, benzyl acetones and phenacyl ethers, respectively, in moderate to good yields at room temperature using diethyl aluminium chloride (Et2AlCl) as a Lewis acid. The Royal Society of Chemistry 2013.
Olefin cross-metathesis/Suzuki-Miyaura reactions on vinylphenylboronic acid pinacol esters
Baltus, Christine B.,Chuckowree, Irina S.,Press, Neil J.,Day, Iain J.,Coles, Simon J.,Tizzard, Graham J.,Spencer, John
supporting information, p. 1211 - 1217 (2013/03/13)
A series of alkenyl phenylboronic acid pinacol esters has been synthesized via an olefin cross-metathesis reaction of vinylphenylboronic acid pinacol ester derivatives. After catalytic hydrogenation, the resulting boronates were coupled via a microwave-mediated Suzuki-Miyaura reaction to afford a library of biarylethyl aryl and biarylethyl cycloalkyl derivatives. A complementary reaction sequence involved an initial Suzuki-Miyaura coupling.
