260352-12-3Relevant academic research and scientific papers
Controlled Reduction of Nitriles by Sodium Hydride and Zinc Chloride
Chiba, Shunsuke,Ong, Derek Yiren
, p. 1369 - 1378 (2020/04/27)
A new protocol for the controlled reduction of nitriles to aldehydes was developed using a combination of sodium hydride and zinc chloride. The iminyl zinc intermediates derived from aromatic nitriles could be further functionalized with allylmetal nucleophiles to afford homoallylamines. As the method allows the reduction of various aliphatic and aromatic nitriles with a concise procedure under milder reaction conditions and exhibits wide functional group compatibility, it is well suited for use in various opportunities in chemical synthesis.
Iminoxyl radical-promoted dichotomous cyclizations: Efficient oxyoximation and aminooximation of alkenes
Peng, Xie-Xue,Deng, Yun-Jing,Yang, Xiu-Long,Zhang, Lin,Yu, Wei,Han, Bing
supporting information, p. 4650 - 4653 (2015/01/08)
A novel iminoxyl radical-involved metal-free approach to vicinal oxyoximation and aminooximation of unactivated alkenes is developed. This method utilizes the dichotomous reactivity of the iminoxyl radical to furnish a general difunctionalization on alkenes using simple tert-butyl nitrite (TBN) as the iminoxyl radical initiator as well the carbon radical trap. By using this protocol, oxime featured 4,5-dihydroisoxazoles and cyclic nitrones were facilely prepared from β,γ- and γ,δ-unsaturated ketoximes, respectively.
Inorganic-base-mediated hydroamination of alkenyl oximes for the synthesis of cyclic nitrones
Peng, Xingao,Tong, Benny Meng Kiat,Hirao, Hajime,Chiba, Shunsuke
supporting information, p. 1959 - 1962 (2014/03/21)
A method based on hydroamination mediated by inorganic base was developed for the synthesis of cyclic nitrones from alkenyl oximes. DFT calculations of the reaction pathway suggested that this hydroamination could proceed through an unprecedented nucleophilic amination of the unactivated alkene by the oxime nitrogen atom. The transition state of this reaction is stabilized by an ionic interaction between a metal cation such as K+ and the oxime oxygen and negatively charged alkene moiety. Basic ring building: A method for the synthesis of cyclic nitrones by using alkenyl oximes was developed based on hydroamination mediated by an inorganic base. DFT calculations for the reaction pathway suggested that this hydroamination could proceed through nucleophilic amination of the unactivated alkene by the oxime nitrogen atom, with the transition state stabilized by ionic interaction with a metal cation such as K+. Copyright
Enantioselective thiourea-catalyzed intramolecular cope-type hydroamination
Brown, Adam R.,Uyeda, Christopher,Brotherton, Carolyn A.,Jacobsen, Eric N.
supporting information, p. 6747 - 6749 (2013/06/05)
Catalysis of Cope-type rearrangements of bis-homoallylic hydroxylamines is demonstrated using chiral thiourea derivatives. This formal intramolecular hydroamination reaction provides access to highly enantioenriched α-substituted pyrrolidine products and represents a complementary approach to metal-catalyzed methods.
A convenient and efficient route for the allylation of aromatic amines and α-aryl aldehydes with alkynes in the presence of a Pd(0)TPhCOOH combined catalyst system
Patil, Nitin T.,Wu, Huanyou,Kadota, Isao,Yamamoto, Yoshinori
, p. 8745 - 8750 (2007/10/03)
The allylation of aromatic amines with alkynes proceeded smoothly in the presence of catalytic amounts of Pd(PPh3)4 and benzoic acid. The allylation products were obtained in high yields in a regio- and stereoselective manner. The effect of various groups on the nitrogen atom of anilines was studied. Regardless of the substituent (electron withdrawing or electron donating) on the aromatic ring, the reaction proceeded well. Various functionalities, including -CH3, -OMe, -Cl, -CN, -COOMe, -NO 2 and -COCH3 were tolerated under the reaction conditions. Similarly, the allylation of α-aryl aldehydes proceeded well with the same level of regio- and stereoselectivity as the allylation of aromatic amines. This reaction provides the second example of the transition metal catalyzed direct α-allylation of aldehydes.
Mechanism of oxygen transfer in the epoxidation of an olefin by molecular oxygen in the presence of an aldehyde
Jarboe, Stephen G.,Beak, Peter
, p. 357 - 360 (2007/10/03)
(formula presented) The reaction pathway for peroxide-initiated aldehyde-mediated oxidation of olefins to epoxides by molecular oxygen has been studied. The pathways of reaction via a peroxy acid or an acyl peroxy radical have been differentiated by investigation of the reaction of 4 with oxygen to provide 6 via 8.
