50397-92-7Relevant academic research and scientific papers
Ambiphilic Reactivity of Vinyl Pd-Oxyallyl for Expeditious Construction of Highly Functionalized Cyclooctanoids
Zuo, Linhong,Ma, Pengchen,Liu, Teng,Chen, Xiangyang,Lavroff, Robert H.,Chen, Wei-Peng,Houk,Guo, Wusheng
supporting information, p. 7330 - 7335 (2021/10/01)
We report the catalytic generation of a vinyl Pd-oxyallyl that dimerizes regiospecifically to form highly functionalized nonbridged cyclooctanoids. Such compounds are otherwise synthetically challenging, but highly useful in synthesis. This vinyl Pd-oxyallyl species demonstrates both electrophilic and nucleophilic properties. DFT calculations elucidate the mechanism and the origins of the chemoselective cyclooctanoid formation.
Iodine-Catalyzed Iso-Nazarov Cyclization of Conjugated Dienals for the Synthesis of 2-Cyclopentenones
Marsili, Lucía A.,Pergomet, Jorgelina L.,Gandon, Vincent,Riveira, Martín J.
supporting information, p. 7298 - 7303 (2018/11/25)
Molecular iodine was identified as an efficient catalyst for the cycloisomerization of conjugated dienals to substituted 2-cyclopentenones. DFT calculations suggested an unexpected concerted character for this cyclization.
Gold(I)-catalyzed divergence in the preparation of bicyclic enol esters: From exclusively [3C+2C]-cycloaddition reactions to exclusive formation of vinylcyclopropanes
Conyers, Ryan C.,Gung, Benjamin W.
, p. 654 - 664 (2013/02/25)
With the use of benzonitrile-stabilized AuI catalyst [Au(IPr)(NCPh)]SbF6 (Ic; IPr=1,3-bis(2,6-diisopropylphenyl)imidazol- 2-ylidene), a spectrum of reactivity is observed for propargyl ester 4 a with cyclic vinyl ethers, ranging from exclusively [3C+2C] cycloaddition reactions to exclusively cyclopropanation depending only on the structure of the substrate. Some initially formed cyclopropanation products rearrange into the corresponding formally [3C+2C] cycloaddition products after treatment with fresh Au I complex at 80 °C. Vinylcyclopropanes formed from dihydrofuran and dihydropyran resisted such rearrangement, even in the presence of fresh AuI catalyst at elevated temperature. This study addresses an important mechanistic question concerning whether the five-membered-ring products were produced by a direct [3C+2C] cycloaddition reaction or by a sequential cyclopropanation/ring-expansion reaction. A dual pathway is proposed for the AuI-catalyzed reactions between propargyl esters and cyclic vinyl ethers. The different behavior among vinyl cyclic ethers is attributed to the difference in the polarization of the π bond. Highly polarized bonds appear to undergo the cycloaddition reaction whereas less polar π-bonds produce cyclopropanes. Copyright
Oxidative conversion of silyl enol ethers to α,β-unsaturated ketones employing oxoammonium salts
Hayashi, Masaki,Shibuya, Masatoshi,Iwabuchi, Yoshiharu
, p. 154 - 157 (2012/02/16)
The oxidative conversion of silyl enol ethers to α,β-unsaturated ketones using a less-hindered class of oxoammonium salts (AZADO +BF4-) is described. The reaction proceeds via the ene-like addition of oxoammonium salts to silyl enol ethers.
Synthesis of cyclopentenols and cyclopentenones via nickel-catalyzed reductive cycloaddition
Jenkins, Aireal D.,Herath, Ananda,Song, Minsoo,Montgomery, John
supporting information; experimental part, p. 14460 - 14466 (2011/11/04)
Strategies for the reductive cycloaddition of enals or enoates with alkynes have been developed. The enal-alkyne cycloaddition directly affords cyclopentenols, whereas the enoate-alkyne cycloaddition affords the analogous cyclopentenones. The mechanism of
Rauhut-Currier type homo- and heterocouplings involving nitroalkenes and nitrodienes
Shanbhag, Pramod,Nareddy, Pradeep R.,Dadwal, Mamta,Mobin, Shaikh M.,Namboothiri, Irishi N. N.
supporting information; experimental part, p. 4867 - 4873 (2010/11/17)
Reaction of nitroalkenes or nitrodienes with methyl vinyl ketone (MVK) or acrylate in the presence of the imidazole-LiCl catalyst system provides Rauhut-Currier (vinylogous Morita-Baylis-Hillman) adducts in moderate yield. Under similar conditions (imidaz
The palladium-catalyzed aerobic kinetic resolution of secondary alcohols: Reaction development, scope, and applications
Ebner, David C.,Bagdanoff, Jeffrey T.,Ferreira, Eric M.,McFadden, Ryan M.,Caspi, Daniel D.,Trend, Raissa M.,Stoltz, Brian M.
supporting information; experimental part, p. 12978 - 12992 (2010/06/19)
The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23°C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-toexcellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.
CuCl-catalyzed reaction of zirconacyclopentenes with oxalyl chloride: a new pathway for the preparation of cyclopentenones
Chen, Chao,Liu, Yundong,Xi, Chanjuan
supporting information; experimental part, p. 5434 - 5436 (2009/12/06)
Zirconacyclopentenes, which are easily prepared from alkynes and EtMgBr (or ethylene) and Cp2ZrCl2, reacted with oxalyl chloride in the presence of catalytic amount of CuCl to give cyclopentenones in high yields. The reaction was per
Palladium-catalyzed enantioselective oxidation of chiral secondary alcohols: Access to both enantiomeric series
Ebner, David C.,Trend, Raissa M.,Genet, Cedric,McGrath, Matthew J.,O'Brien, Peter,Stoltz, Brian M.
scheme or table, p. 6367 - 6370 (2009/03/11)
(Chemical Equation Presented) Rapid resolution: A new catalyst system for the oxidative kinetic resolution of secondary alcohols leads to dramatic rate increases. This system allows the use of a diamine to provide access to either enantiomer of a range of alcohols with good selectivity factors (see scheme). This method has been applied to the formal total synthesis of (-)-amurensinine.
Palladium(0)-catalyzed Suzuki-Miyaura cross-coupling reactions of potassium aryl- and heteroaryltrifluoroborates with alkenyl bromides
Molander, Gary A.,Fumagalli, Tiziano
, p. 5743 - 5747 (2007/10/03)
Efficient palladium(0)-catalyzed Suzuki-Miyaura cross-couplings are described. The reactions involving potassium aryl- and heteroaryltrifluoroborates with alkenyl bromides can generally be carried out using ≤2 mol % of palladium catalyst and 3 equiv of ba
