• Bulletin of the Korean Chemical Society
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• 제17권8호
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• pp.725-729
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• 1996

Reaction of carbonyl compounds with B-alkoxydiisopinocampheylborane (Ipc2BOR, R=H, Et, i-Pr, t-Bu) was investigated in detail in order to establish their usefulness as selective reducing agents. The reagents were extremely mild and reduced only aldehydes effectively under mild conditions. The reagents also reduced α,β-unsaturated aldehydes to the corresponding allylic alcohols without any detectable 1,4-reduction. Furthermore, aldehydes can be reduced in the presence of epoxides and acid chlorides. Consequently, the selective reduction of aldehyde groups in the presence of keto and all other functional groups has been realized with these reagents.

• Bulletin of the Korean Chemical Society
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• 제8권5호
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• pp.414-418
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• 1987

Electrochemical reduction of dibenzoylmethane was studied on mercury electrode by means of cyclic voltammetry, polarography and potentiostatic measurements in ethanol-water system. In acidic solutions monomeric pinacol was produced by irreversible two-electron process while monomeric and dimeric pinacol were competitively produced by the same process in neutral solution. However, in basic solution the dimeric pinacol was mostly produced through radical by irreversible one-electron transfer process. Mechanisms of the reduction of dibenzoylmethane are deduced from Tafel slope, pH dependance and reaction order with respect to the concentration of dibenzoylmethane in the solution of various pH.

• Bulletin of the Korean Chemical Society
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• 제8권3호
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• pp.202-205
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• 1987

The reduction of some cyclic conjugated enones with electron-donating substituent on C-3 by sodium borohydride was accelerated on irradiation. The photo-enhanced reduction seems to undergo through zwitterionic species formed from the (n, ${\pi}^{\ast}$) triplet state of conjugated enones, followed by hydride attack to yield unsaturated or saturated alcohols.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2162-2190
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• 2007

The newly-developed Meerwein-Ponndorf-Verley (MVP) type reagents using aluminum, boron and other metals for reduction of organic functional groups such as carbonyl and epoxy compounds have been surveyed. highlighted and reviewed in this account are the appearance of new MPV type reagents and their application to the selective reduction of organic functions. Finally, this account emphasizes the distinct contrast in the reducing characteristics existed between metal hydride reagents and MPV reagents, and compares their usefulness in organic synthesis.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.546-550
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• 2014

Relative reactivity of various carbonyl and acid derivatives in MPV-type (Meerwein-Ponndorf-Verley) reduction with an DIBAL(F) model has been studied via DFT and MP2 methods. Free energies of initial adduct formation (-Gadd) of DIBAL(F) model and carbonyls are in the order of amide < ester < aldehyde < ketone < acid chloride; in the alan-amide adduct, the developed positive charge at carbonyl carbon is expected to be stabilized by amide resonance, but in the acid chloride adduct it is destabilized by inductive effect of chloride. However the TS barrier energies (${\Delta}G_{TS}$) for the MPV-type hydride reduction of the carbonyl adducts are in the order of aldehyde < ketone < acid chloride << ester < amide; presumably decreasing order of electrophilicity of carbonyl carbon at adducts, which is well correlated with experimental data. It is noted that the relative reactivity of carbonyl derivatives in MPV-type reduction with DIBAL(X) is not governed by the alan-adduct formation energies, but follows the order of electrophilicity of carbonyl carbon of transition states.

• Bulletin of the Korean Chemical Society
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• 제32권1호
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• pp.219-224
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• 2011

The new MPV type reagent, Al-trifluoromethanesulfonyldiisobutylalane ($DIBAO_3SCF_3$), has been prepared and its reducing characteristics in the reduction of selected organic compounds containing representative functional groups have been examined, and compared its reactivity with that of Al-methanesulfonyldiisobutylalane ($DIBAO_3SCH_3$) in order to understand the fluorine-substituent effect on its reactivity. In general, the reactivity of $DIBAO_3SCF_3$ appears to be much higher than that of $DIBAO_3SCH_3$, apparently due to the acidity increase by the electron-withdrawing fluorine-substituent. The reagent reduced aldehydes and ketones readily, but showed a perfect selectivity in the reduction of $\alpha,\beta$-unsaturated aldehydes and ketones to produce the corresponding allylic alcohols in an absolutely 100% purity. In addition, the reagent achieved the regioselective cleavage of phenyl- or/and alkyl-substituted epoxides to the less substituted alcohols in a perfect regioselectivity. Moreover, the reagent also showed an high stereoselectivity in the reduction of substituted cycloalkanones to produce the thermodynamically more stable alcohol epimers exclusively.

• Bulletin of the Korean Chemical Society
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• 제31권4호
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• pp.840-844
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• 2010

The new MPV type reagent, Al-methanesulfonyldiisobutylalane ($DIBAO_3SCH_3$), has been prepared and its reducing characteristics in the reduction of selected organic compounds containing representative functional groups have been examined in order to find out a new reducing system with high selectivity in organic synthesis. In general, the reagent is extremely mild, showing only reactivity toward aldehydes, ketones and epoxides. The reagent exhibits a unique reducing applicability in organic synthesis. Thus, the reagent can achieve a clean 1,2-reduction of $\alpha,\beta$-unsaturated aldehydes and ketones to produce the corresponding allylic alcohols in 100% purity. In addition, the reagent shows an excellent regioselectivity in the ring-opening reaction of epoxides. Finally, $DIBAO_3SCH_3$ shows a high stereoselectivity in the reduction of cyclic ketones to produce the thermodynamically more stable epimers exclusively.

• Bulletin of the Korean Chemical Society
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• 제27권11호
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• pp.1763-1768
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• 2006

The application of poly(Co(II)-(1,8-diaminonaphthalene))(poly(Co-DAN)) and poly(1,8-diaminonaphthalene) (Poly(1,8-DAN)) to the electrocatalytic reduction of molecular oxygen was investigated, which were electrochemically grown by the potential cycling method on the glassy carbon electrodes. The reduction of oxygen at the polymer and its metal complex polymer coated electrodes were irreversible and diffusion controlled. The Poly(1,8-DAN) and Poly(Co-DAN) films revealed the potential shifts for the oxygen reduction to 30 mV and 110 mV, respectively, in an aqueous solution, compared with that of the bare electrode. Hydrodynamic voltammetry with a rotating ring-disk electrode showed that Poly(1,8-DAN) and Poly(Co-DAN) coated electrodes converted respectively 84% and 22% of $O_2$ to $H_2O$ via a four electron reduction pathway.

• Bulletin of the Korean Chemical Society
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• 제17권10호
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• pp.885-892
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• 1996

The effects of NOx reduction by advanced fuel staging in a small scale combustor (6.6 kWT) have been investigated using propane gas flames laden with ammonia as fuel-nitrogen. The variables which had the greatest influence on NOx reduction were temperature, reducing stoichiometry (relate to main combustion zone stoichiometry, air fraction and reburning fuel fraction) and residence time of reducing zone. NOx reduction was best at the reburning zone temperature of above 1,000 ℃ and reburning zone stoichiometry was 0.85. In terms of residence time of the reburning zone, NOx reduction was effective when burnout air was injected at the point where the reburning zone had been already established. In the advanced fuel staging NOx reduction was relatively large at the burning of higher Fuel-N concentration in the fuel. Under optimum reburning conditions, fuel nitrogen content had a relatively minor impact on reburning efficiency.

• Bulletin of the Korean Chemical Society
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• 제19권4호
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• pp.417-422
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• 1998

The electrocatalytic reduction of molecular oxygen was investigated with a Co(II)-glyoxal bis(2-hydroxyanil) complex coated-glassy carbon (GC) electrode in aqueous media. The reduction of $O_2$ at the modified electrode was an irreversible and diffusion-controlled reaction. The complex coated-GC electrode demonstrated an excellent electrocatalytic effect for $O_2$ reduction in an acetate buffer solution of pH 3.2. The coated electrode made the $O_2$ reduction potential shift of 60-510 mV in a positive direction compared to the bare GC electrode depending on pH. The Co(II)-glyoxal bis(2-hydroxyanil) coated electrode converted about 51% of the $O_2$ to $H_2O_2$ via a two-electron reduction pathway, with the balance converted to H_2O$.