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Hydride transfer method

Recently, a variety of (3-silylated carboxonium ions have been prepared and characterized by NMR spectroscopy.541 Kira et al.631 used the Corey hydride transfer method, whereas Olah, Prakash, and co-workers applied triphenylmethyl tetrakis (pentafluorophenyl)borate to silylate esters,632 ketones, enones, and carbonates633 [Eq. (3.91)]. The ions thus produced are resonance hybrids of oxocarbenium (327b) and carboxonium (327a) ions with the latter as the major contributors. Calculated (DFT/IGLO) 29 Si NMR chemical shifts agree well with the experimental data. [Pg.188]

As a result of the conclusions reached in these studies, a simple competition method was devised 12, 32) to determine relative rates of hydride transfer reactions rather accurately. For example, to obtain relative reaction rates of ethyl ions with various additives, a suitable source of fully deuterated ethyl ions such as C3D8 or iso-C4Di0 was irradiated in the presence of a perprotonated additive (RH), leading to the formation of C2D6 and C2D5H by Reactions 2 and 3. [Pg.272]

The regiochemical control of Pd-catalyzed hydride transfer reaction is much more effective than that of the radical denitration, as shown in Eq. 7.98. The base-catalyzed reaction of nitroolefins with aldehydes followed by denitration provides a new synthetic method of homoallyl alcohols (Eq. 7.99).140 Exomethylene compounds are obtained by denitration of cyclic allylic nitro compounds with Pd(0), HC02H and Et3N (Eq. 7.100).140b... [Pg.213]

To better understand the catalytic mechanism of DHFR and to use this information for the design of potent DHFR-specific inhibitors, we evaluated the proton and hydride transfers using an integrated ab initio Quantum Mechanics/Molecular Mechanics (QM/MM) approach in combination with FEP technology. The combinatorial application of these methods enabled us to propose a precise path along which the proton and hydride ion are transferred and to address the key structural and energetic changes associated with catalysis. [Pg.255]

The reactions of the species H3O+, NO+, and O2+ with a range of aldehydes and ketones have been studied by the selected ion flow tube (SIFT) method. H3O+ protonates ketones and aldehydes, with the latter eliminating water under the conditions of measurement. Similarly, NO+ associates with ketones, but this is followed by hydride transfer for the aldehydes. O2+ reactions typically produce several ionic products. [Pg.29]

The major obstacle of the hydride transfer reaction is the steric bulk of the trityl cation as the reagent of choice. Substrates that will allow the isolation of cations RsE, free from intramolecular and/or intermolecular interactions with solvent molecules or anions, need to have bulky substituents and therefore the hydride transfer reaction between the hydride and trityl cation is severely hampered or it is even impossible. Another drawback of this method is the limited availability of the starting hydrido compound, which for example, is not available for lead compounds, due to the high reactivity of lead(IV) hydrides. [Pg.158]

According to further papers from Gronowitz etal. [70ZC389 73ACS2257, 73CS(3)165 78JHC285], the reduction of other tricyclic tropones does not require the presence of a Lewis acid. This might be due to the stability (see Section III,B,3,b) of the carbenium ions (formed from the intermediate tropols), which are further reduced to the tropilidenes by hydride transfer. For example, tropylium ions 237 and 238 can be prepared by this method. [Pg.134]

A number of methods have been utilized to probe hydride transfer reactions. These include the efforts to follow the course of the reaction in deuterated or tritiated water. Perhaps one of the most effective methods is to study isotope effects. ... [Pg.349]

Other methods are also available for generation of boron enolates. Dialkylboranes react with acyclic enones to give Z-enolates by a 1,4-reduction.19 The preferred Z-stereochemistry is attributed to a cyclic mechanism for hydride transfer ... [Pg.72]

Disproportionation has been observed frequently with thiopyrans and rarely with 4//-pyrans, and all cases involve a tetragonal carbon center (position 2 or 4) bearing at least one C—H bond. Some molecules of the substrate are aromatized to corresponding thiopyrylium or pyrylium ions and others reduced to dihydro or tetrahydro products. The relative abilities of pyrans and thiopyrans to disproportionate were interpreted within a proposed hydride transfer mechanism by a CNDO/2 method.45... [Pg.241]


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See also in sourсe #XX -- [ Pg.158 ]

See also in sourсe #XX -- [ Pg.158 ]




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