786-08-3Relevant academic research and scientific papers
Photoelimination of Nitrogen from Diazoalkanes: Involvement of Higher Excited Singlet States in the Carbene Formation
Pite?a, Tomislav,Ale?kovi?, Marija,Becker, Kristin,Basari?, Nikola,Do?li?, Nada
, p. 9718 - 9724 (2020/07/02)
Although diazoalkanes are important carbene precursors in organic synthesis, a comprehensive mechanism of photochemical formation of carbenes from diazoalkanes has not been proposed. Synergies of experiments and computations demonstrate the involvement of higher excited singlet states in the photochemistry of diazoalkanes. In all investigated diazoalkanes, excitation to S1 results in nonreactive internal conversion to S0. On the contrary, excitation to higher-lying singlet states (Sn, n > 1) drives the reaction toward a different segment of the S1/S0 conical intersection seam and results in nitrogen elimination and formation of carbenes.
Alkyllithium Compounds Bearing Electrophilic Functional Groups: A Flash Chemistry Approach
Nagaki, Aiichiro,Yamashita, Hiroki,Hirose, Katsuyuki,Tsuchihashi, Yuta,Yoshida, Jun-ichi
supporting information, p. 4027 - 4030 (2019/02/24)
Flash chemistry based on flow microreactor systems allowed alkyllithiums bearing electrophilic functional groups to be successfully generated and used for subsequent reactions. The series of reactions with high reactivity was achieved by extremely accurate control over residence time in a controlled and selective manner.
Asymmetrie allylation of methyl ketones by using chiral phenyl carbinols
Tietze, Lutz F.,Kinzel, Tom,Wolfram, Thomas
experimental part, p. 6199 - 6210 (2010/03/01)
Novel chiral auxiliaries for the stereoselective allylation of aliphatic methyl ketones with allyltrimethylsilane and their use in the synthesis of homoallylic ethers are described. In a multicomponent domino process catalyzed by trifluoromethanesulfonic
Asymmetric induction during electron transfer mediated photoreduction of carbonyl compounds: Role of zeolites
Shailaja,Kaanumalle, Lakshmi S.,Sivasubramanian, Karthikeyan,Natarajan, Arunkumar,Ponchot, Keith J.,Pradhan, Ajit,Ramamurthy
, p. 1561 - 1571 (2008/02/03)
Photochemistry of 17 aryl alkyl ketones included within cation exchanged zeolites has been examined. In solution five of the 17 ketones undergo intramolecular hydrogen abstraction reaction even in the presence of a chiral amine and the rest are photoreduced to the corresponding alcohol. Within zeolites all 17 ketones yielded in presence of a chiral amine, the corresponding alcohol as the major product. When a chiral amine was used as the coadsorbent within alkali ion exchanged zeolites, enantiomerically enriched alcohol was formed in all cases. The best chiral induction was obtained with phenyl cyclohexyl ketone (enantiomeric excess: 68%). 1H-13C Cross Polarization Magic Angle Spinning (CP-MAS) experiments, with a model ketone (perdeuterated acetophenone) and chiral amine (pseudoephedrine) included within MY zeolites, suggested that the cation brings the reactant and the chiral amine closer. The role of the cation in such a process is also revealed by the computation results. The results presented here highlight the importance of a supramolecular structure in forcing a closer interaction between a reactant and a chiral inductor that could be used to achieve asymmetric induction in photoproducts. The Royal Society of Chemistry 2006.
Formation of Cage-Structure Organomagnesium Compounds. Influence of the Degree of Adsorption of the Transient Species at the Metal Surface
Molle, G.,Bauer, P.,Dubois, J. E.
, p. 4120 - 4128 (2007/10/02)
Secondary and tertiary adamantyl organomagnesium compounds have been synthesized with yields of ca. 60percent by means of an original static procedure.By condensing Grignard reagents of adamantane over benzaldehyde, 70percent and 72percent yields of alcohol are obtained; the 1- and 2-adamantanecarboxylic acid chlorides give 40percent and 50percent yields of 1,1- and 2,2-diadamantyl ketone, respectively.Competition between the various reactions occuring either at the metal-solution interface (formation of the organomagnesium compound and of the dimerization hydrocarbon) or in the medium (formation of the solvent-attack products) is studied in terms of the stirring, the nature of the halogen, the basicity of the solvent, and the ratio of the magnesium surface to the halide.The kinetic study of the formation of these organomagnesium compounds demonstrates the essential role of the anion radical (RX) and of radical pair (RMgX), whose degrees of adsorption at the metal surface, i.e., electrostatic interaction between the transient species at the metal surface, after the single electron transfer (SET), determine the competition between the various reaction pathways.These degrees of adsorption are highly dependent on the nature of the cage structure of the radical.An XPS analysis at different depths of the deposit at the metal surface provides invaluable information on the phenomena occuring at the metal-solution interface when 1-bromoadamantane attacks the magnesium.This makes it possible to retrace the history of the reaction in its initial phase.
Hypobetalipoproteinemic agents. II. Compounds related to 4-(1- adamantyloxy)aniline
Lednicer,Heyd,Emmert,et al.
, p. 69 - 77 (2007/10/06)
While the previously used displacement reaction of sodium 1-adamantyl oxide on 4-fluoronitrobenzene was applicable to the preparation of 4-(1-adamantyloxy) aniline and several related compounds, certain derivatives were not easily accessible by this route
Polycyclophenylpyrrolidines, their compositions and use
-
, (2008/06/13)
Compounds of the formula STR1 where R4 X is a polycyclocoupled group and R1 and R2 are H or simple hydrocarbon and R3 has the same value and additionally simple acyl, can be made by a variety of syntheses. They have hypolipedemic and antiatherosclerotic properties, and are useful in that field.
