Reduction ketones, mechanism

Kejrwords Dynamic kinetic asymmetric transformation (DYKAT) Dynamic kinetic resolution (DKR) Hydrogenation Imine reduction Ketone reduction Mechanism of carbonyl reduction Mechanism of imine reduction Mechanism of dUiydrogen activation Ruthenium catalysis Shvo s catalyst Transfer hydrogenation... 

Sodium borohydride and lithium aluminum hydride react with carbonyl compounds in much the same way that Grignard reagents do except that they function as hydride donors rather than as carbanion sources Figure 15 2 outlines the general mechanism for the sodium borohydride reduction of an aldehyde or ketone (R2C=0) Two points are especially important about this process... 

The mechanism of lithium aluminum hydride reduction of aldehydes and ketones IS analogous to that of sodium borohydride except that the reduction and hydrolysis... 

FIGURE 15 2 Mechanism of sodium borohydnde reduction of an aldehyde or ketone... 

The 1990 Clean Air Act Amendments Hst 189 hazardous air pollutants (HAPs) that the EPA must regulate to enforce maximum achievable control technology (MACT) to standards which are to be set by the year 2000. The 33/50 project calls for reduction of emissions of 17 specified solvents to predetermined levels by 1995. The SARA statute provides a mechanism by which the community can be informed of the existence, quantities, and releases of toxic chemicals, and requires that anyone releasing specific toxic chemicals above a threshold level to annually submit a toxic chemical release form to the EPA. The status of various ketones under these regulations is shown in Table 4. 

A recently discovered reduction procedure provides a convenient route to axial alcohols in cyclohexyl derivatives (5). The detailed mechanism of the reaction remains to be elucidated, but undoubtedly the reducing agent is an iridium species containing one or more phosphate groups as ligands. In any case, it is clear that the steric demands of the reducing agent must be extraordinary since the stereochemical outcome of the reaction is so specific. The procedure below is for the preparation of a pure axial alcohol from the ketone. 

Figure 17.8 The biologi-cal oxidation of an alcohol (sn-glycerol 3-phosphate) to give a ketone dihydroxy-acetone phosphate). This mechanism is the exact opposite of the ketone reduction shown previously in Figure 17.4.

Figure 19.15 Mechanism of biological aldehyde and ketone reductions by the coenzyme NADH.

The Mecrwein-Ponndoi f-Verlev reaction involves reduction of a ketone by treatment with an excess of aluminum triisopropoxide. The mechanism of the process is closely related to the Cannizzaro reaction in that a hydride ion acts as a leaving group. Propose a mechanism. 

The mechanism of this Grignard reaction is similar to that of L1AIH4 reduction. The first equivalent of Grignard reagent adds to the acid chloride, loss of (T from the tetrahedral intermediate yields a ketone, and a second equivalent of Grignard reagent immediately adds to the ketone to produce an alcohol. 

Active Figure 24.4 MECHANISM Mechanism of reductive amination of a ketone to yield an amine. Details of the imine-forming step were shown in Figure 19.8 on page 711. Sign in afwww.thomsonedu.com to see a simulation based on this figure and to take a short quiz. 

The mechanism for the transformation of 5 to 4 was not addressed. However, it seems plausible that samarium diiodide accomplishes a reduction of the carbon-chlorine bond to give a transient, resonance-stabilized carbon radical which then adds to a Smni-activated ketone carbonyl or combines with a ketyl radical. Although some intramolecular samarium(n)-promoted Barbier reactions do appear to proceed through the intermediacy of an organo-samarium intermediate (i.e. a Smm carbanion),10 ibis probable that a -elimination pathway would lead to a rapid destruction of intermediate 5 if such a species were formed in this reaction. Nevertheless, the facile transformation of intermediate 5 to 4, attended by the formation of the strained four-membered ring of paeoniflorigenin, constitutes a very elegant example of an intramolecular samarium-mediated Barbier reaction. 

D. C. Wigeield, Stereochemistry and Mechanism of Ketone Reductions by Hydride Reagents, Tetrahedron 35,449 (1979). 

The most plausible mechanism for the interconversion of la and Ih is shown in Scheme 2. Similar mechanism has been put forward for epimerization of a-substituted ketones under basic conditions and for the equilibration via an enolate prior to nucleophilic substitution was observed by Numazawa et al. (ref. 13). The same mechanism seems to operate in the reduction of some steroid a-haloketones (ref. 14) or tra/ty-3-chloroflavanone (ref. 15) with sodium borohydride where an inversion of configuration takes place at the a carbon parallel to the reduction of the... 

Sn 1 mechanism. The reaction can also be applied to primary and secondary alcohols if these contain an aryl group in the a position. Higher trialkylaluminums are far less suitable, because reduction competes with alkylation (see also reactions of Me3Al with ketones, 16-27, and with carboxylic acids, 16-33). The compound Me2TiCl2... 

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