74793-18-3Relevant academic research and scientific papers
Functionalized styrene synthesis via palladium-catalyzed C[sbnd]C cleavage of aryl ketones
Dai, Hui-Xiong,Wang, Xing,Wang, Zhen-Yu,Xu, Hui,Zhang, Xu
, (2022/03/31)
We report herein the synthesis of functionalized styrenes via palladium-catalyzed Suzuki–Miyaura cross-coupling reaction between aryl ketone derivatives and potassium vinyltrifluoroborate. The employment of pyridine-oxazoline ligand was the key to the cleavage of unstrained C[sbnd]C bond. A variety of functional groups and biologically important moleculars were well tolerated. The orthogonal Suzuki–Miyaura coupling demonstrated the synthetic practicability.
Nickel-Catalyzed Ring-Opening Allylation of Cyclopropanols via Homoenolate
Sekiguchi, Yoshiya,Lee, Yan Ying,Yoshikai, Naohiko
supporting information, p. 5993 - 5997 (2021/08/16)
We report herein a nickel-catalyzed ring-opening allylation of cyclopropanols with allylic carbonates that occurs under mild and neutral conditions. The reaction displays linear selectivity for both linear and branched acyclic allylic carbonates and is also applicable to cyclic allylic carbonates, affording a variety of δ,?-unsaturated ketones in moderate to good yields. Mechanistic experiments are in accord with a catalytic cycle involving decarboxylative oxidative addition of allylic carbonate to Ni(0), alkoxide exchange with cyclopropanol, cyclopropoxide-to-homoenolate conversion on Ni(II), and C-C reductive elimination.
Nickel-catalyzed Heck reaction of cycloalkenes using aryl sulfonates and pivalates
Zhou, Jianrong Steve,Huang, Xiaolei,Teng, Shenghan,Chi, Yonggui Robin
supporting information, p. 3933 - 3936 (2021/04/26)
Nickel-catalyzed Heck reaction of cycloalkenes delivers unusual conjugated arylated isomers. Nickel(0) catalysts ligated by chelating dialkylphosphines effectively activate not only aryl triflates as electrophiles, but also less reactive aryl mesylates, t
Regio- and enantioselective Baeyer-Villiger oxidation: Kinetic resolution of racemic 2-substituted cyclopentanones
Zhou, Lin,Liu, Xiaohua,Ji, Jie,Zhang, Yuheng,Wu, Wangbin,Liu, Yangbin,Lin, Lili,Feng, Xiaoming
supporting information, p. 3938 - 3941 (2014/08/18)
A kinetic resolution of racemic 2-substituted cyclopentanones via highly regio- and enantioselective Baeyer-Villiger oxidation has been successfully developed. The reaction could afford the normal 6-substituted δ-lactones in up to 98% ee and >19/1 regioselectivity. Meanwhile, the unreacted ketones were recovered in excellent ee values (up to 98%). It represents the best results of the kinetic resolution of racemic 2-substituted cyclopentanones via nonenzymic asymmetric BV oxidation.
Mechanistic switch via subtle ligand modulation: Palladium-catalyzed synthesis of α,β-substituted styrenes via C-H bond functionalization
Flores-Gaspar, Areli,Martin, Ruben
, p. 1223 - 1228 (2011/06/26)
A new catalyst system able to efficiently perform the synthesis of styrenes via C-H bond functionalization and a subtle ligand modification are described. The high level of activity achieved allows for the synthesis of highly functionalized α,β-substituted styrenes, even the elusive E-configured trisubstituted olefins, in a regio- and stereoselective manner. Mechanistic experiments allowed for the identification of the corresponding synthetic intermediates.
The skeletal rearrangement of gold- and platinum-catalyzed cycloisomerization of cis-4,6-dien-1-yn-3-ols: Pinacol rearrangement and formation of bicyclo[4.1.0]heptenone and reorganized styrene derivatives
Tang, Jhih-Meng,Bhunia, Sabyasachi,Sohel, Shariar Md. Abu,Lin, Ming-Yuan,Liao, Hsin-Yi,Datta, Swarup,Das, Arindam,Liu, Rai-Shung
, p. 15677 - 15683 (2008/09/19)
With gold and platinum catalysts, cis-4,6-dien-1-yn-3-ols undergo cycloisomerizations that enable structural reorganization of cyclized products chemoselectively. The AuCl3-catalyzed cyclizations of 6-substituted cis-4,6-dien-1-yn-3-ols proceeded via a 6-exo-dig pathway to give allyl cations, which subsequently undergo a pinacol rearrangement to produce reorganized cyclopentenyl aldehyde products. Using chiral alcohol substrates, such cyclizations proceed with reasonable chirality transfer. In the PtCl 2-catalyzed cyclization of 7,7-disubstituted cis-4,6-dien-1-yn-3-ols, we obtained exclusively either bicyclo-[4.1.0]heptenones or reorganized styrene products with varied substrate structures. On the basis of the chemoselectivity/structure relationship, we propose that bicyclo[4.1.0]heptenone products result from 6-endo-dig cyclization, whereas reorganized styrene products are derived from the 5-exo-dig pathway. This proposed mechanism is supported by theoretic calculations.
A convenient synthesis of 2-naphthylcyclopentanones and 2-naphthylcyclohexanones from 1-naphthylcycloalkenes
Gora, Maciej,Luczynski, Michal K.,Sepiol, Janusz J.
, p. 1625 - 1630 (2007/10/03)
The oxidation of naphthylcycloalkenes with hydrogen peroxide or MCPBA followed by acid catalyzed rearrangement of diol (epoxide), afforded a series of naphthylcycloalkanones in a very simple manner. The conditions allow preparation of naphthylcycloalkanones on a multigram scale. Georg Thieme Verlag Stuttgart.
Fjord Region 3,4-Diol 1,2-Epoxides and Other Derivatives in the 1,2,3,4- and 5,6,7,8-Benzo Rings of the Carcinogen Benzochrysene
Utermoehlen, Clifford M.,Singh, Mahatam,Lehr, Roland E.
, p. 5574 - 5582 (2007/10/02)
Dihydrodiol and diol epoxide derivatives of the carcinogen benzochrysene (BgCh) have been prepared to probe structural factors involved in the carcinogenesis and mutagenesis of polycyclic aromatic hydrocarbons.Preparation of 1,2-dihydrobenzochrysen-4(3H)-one (6) and 7,8-dihydrobenzochrysen-5(6H)-one (11), ketones suitable for further elaboration to potential metabolites of benzochrysene in the 1,2,3,4- and 5,6,7,8-benzo rings, respectively, was achieved through two cyclization steps.Photochemical closure of 2-(1- or 2-naphthyl)styrene derivatives 4 and 9 aff orded chrysene and benzophenanthrene ring systems with a butyric ester/acid side chain poised for a second ring closure (acid-catalyzed) to the desired ketones.Preparation of pure BgCh 3,4-diol 1,2-epoxides 23 and 24 from the dihydrodiol diester 14 by conversion to separable trans bromohydrins, cyclization to the epoxides, and hydrolysis of the acetates was found to be more successful than preparation from the dihydrodiol 15.
