• Bulletin of the Korean Chemical Society
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• 제33권8호
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• pp.2719-2723
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• 2012

A kinetic study is reported for nucleophilic substitution reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in MeCN. The plot of pseudo-first-order rate constant ($k_{obsd}$) vs. [amine] curves upward, which is typical for reactions reported previously to proceed through a stepwise mechanism with two intermediates (i.e., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). Dissection of $k_{obsd}$ into the second- and third-order rate constants (i.e., $Kk_2$ and $Kk_3$, respectively) reveals that $Kk_3$ is significantly larger than $Kk_2$, indicating that the reactions proceed mainly through the deprotonation pathway (i.e., the $k_3$ process) in a high [amine] region. This contrasts to the recent report that the corresponding aminolysis of benzyl 2-pyridyl carbonate 5 proceeds through a forced concerted mechanism. An intramolecular H-bonding interaction was suggested to force the reactions of 5 to proceed through a concerted mechanism, since it could accelerate the rate of leaving-group expulsion (i.e., an increase in $k_2$). However, such H-bonding interaction, which could increase $k_2$, is structurally impossible for the reactions of 6. Thus, presence or absence of an intramolecular H-bonding interaction has been suggested to be responsible for the contrasting reaction mechanisms (i.e., a forced concerted mechanism for the reaction of 5 vs. a stepwise mechanism with $T^{\pm}$ and $T^-$ as intermediates for that of 6).

• Bulletin of the Korean Chemical Society
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• 제33권7호
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• pp.2269-2273
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• 2012

Pseudo-first-order rate constants $k_{amine}$ have been measured spectrophotometrically for the reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. The plots of $k_{amine}$ vs. [amine] curve upward, indicating that the reactions proceed through a stepwise mechanism with two intermediates, a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$. This contrasts to the report that the corresponding reactions of benzyl 2-pyridyl carbonate 5 proceed through a forced concerted pathway. The $k_{amine}$ values for the reactions of 6 have been dissected into the second-order rate constant $Kk_2$ and the thirdorder rate constant $Kk_3$. The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}=0.94$ and 1.18 for $Kk_2$ and $Kk_3$, respectively. The $Kk_2$ for the reaction of 6 is smaller than the second-order rate constant $k_N$ for the corresponding reaction of 5, although 4-pyridyloxide in 6 is less basic and a better nucleofuge than 2-pyridyloxide in 5.

• EDISON SW 활용 경진대회 논문집
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• 제2회(2013년)
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• pp.101-109
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• 2013

Diels-Alder 반응은 유기합성에서 중요하게 다뤄지는 고리형성 반응으로 위치 선택성과 더불어 단일 단계 반응이기에 특이한 입체 선택성을 갖는 것으로 알려졌다. 그러나 실제로는 단계적 반응 경로도 존재할 수 있음을 발견하였는데, 이 경우에 갖는 위치 선택성과 입체 선택성은 달라질 가능성이 높다. Density Functional Theorem(DFT)로 계산한 결과, 비대칭 Diels-Alder 에 대해 단계적 반응의 경우에도 마찬가지로 유사 ortho 형태에 endo 지향성을 나타내었지만 대칭 Diels-Alder 반응에 비해 단계적 반응이 일어나기 힘들다는 결론을 얻을 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제24권8호
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• pp.1135-1140
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• 2003

The kinetics and mechanism of the pyridinolysis $(XC_5H_4N)$ of Y-aryl phenyl isothiocyanophosphates (1;$(YC_6H_4O)\;(C_6H_5O)$P(=O)NCS) are investigated in acetonitrile at 55.0 ℃. The Hammett plots for substituent (Y) variations in the substrate (log k₂ vs σY) exhibit a convex upward biphasic type with breaks at Y = H. For electron-donating Y groups the Hammett coefficients, ρY, are positive and cross-interaction constant ρXY is negative, while those for electron-withdrawing Y groups ρY values are negative with a positive ρXY. These results are interpreted to indicate mechanistic change at the breakpoint (σY = 0) from a concerted to a stepwise mechanism with rate-limiting expulsion of the $^-NCS$ group from a trigonal bipyramidal pentacoordinated (TBP-5C) intermediate. Biphasic plots of log k₂ vs σX or $pK_a$(X) with steeper slopes for the more basic nucleophiles are obtained suggesting an equatorial nucleophilic attack in contrast to an apical attack for the less basic nucleophiles with smaller magnitude of ρX or βx.

• Bulletin of the Korean Chemical Society
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• 제30권12호
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• pp.2913-2917
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• 2009

Second-order rate constants (k$_{Nu–}$) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-i) with butane-2,3-dione monoximate ($Ox^-\;an\;\alpha$-nucleophile) and Z-substituted phenoxides in 80 mol% H$_2$O/20 mol% DMSO at 25.0${\pm}$0.1$^{\circ}C$. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for reactions of 1a-h with Ox$^–$ exhibit many scattered points. In contrast, the Yukawa-Tsuno plot results in a good linear correlation with ${\rho}_Y$ = 2.20 and r = 0.45, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS). A stepwise mechanism with expulsion of the leaving-group being the RDS has been excluded, since Y-substituted phenoxides are less basic and better nucleofuges than Ox$^–$. Thus, the reactions have been concluded to proceed through a concerted mechanism. Ox$^–$ is over 10$^2$ times more reactive than its reference nucleophile, 4-chlorophenoxide (4-ClPhO$^–$). One might suggest that stabilization of the transition-state (TS) through intramolecular general acid/base catalysis is responsible for the ${\alpha}$-effect since such general acid/base catalysis is not possible for the corresponding reactions with 4-ClPhO$^–$. However, destabilization of the ground-state (GS) of Ox$^–$ has been concluded to be mainly responsible for the ${\alpha}$-effect found in this study on the basis of the fact that the magnitude of the ${\alpha}$-effect is independent of the nature of the substituent Y.

• Bulletin of the Korean Chemical Society
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• 제29권4호
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• pp.851-855
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• 2008

The reactions of O,O-diphenyl Z-S-phenyl phosphorothiolates with X-pyridines have been studied kinetically in acetonitrile at $35.0{^{\circ}C}$. The Hammett plots for substituent (Z) variations in the leaving group (log $k_2$ vs. $\sigma$ Z) are biphasic concave downwards with breaks at Z = H. The large magnitudes of ${\rho}X(\rho_{nuc})$, ${\beta}X(\rho_{nuc})$, and the cross-interaction constant, $\rho$XZ, suggest frontside nucleophilic attack toward the leaving group. The sign reversal of $\rho$Z from positive in $\sigma$ Z $\leq$ 0 to negative in $\sigma$ Z $\geq$ 0 is interpreted as the change in mechanism from concerted to stepwise with rate-limiting expulsion of the leaving group. The anomalous negative sign of $\rho$ Z for leaving groups with electron-withdrawing substituents is interpreted as the intramolecular ligand exchange process of the leaving group from the equatorial position in the intermediate to the apical position in the TS.

• Bulletin of the Korean Chemical Society
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• 제35권1호
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• pp.177-181
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the reactions of Y-substituted-phenyl benzoates (5a-j) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [EtOK] curve upward regardless of the electronic nature of the substituent Y in the leaving group. Dissection of $k_{obsd}$ into the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOK (i.e., $k_{EtO^-}$ and $k_{EtOK}$, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The Br${\phi}$nsted-type plots for the reactions with the dissociated $EtO^-$ and ion-paired EtOK exhibit highly scattered points with ${\beta}_{lg}$ = -$0.5{\pm}0.1$. The Hammett plots correlated with ${\sigma}^o$ constants result in excellent linear correlations, indicating that no negative charge develops on the O atom of the leaving Y-substituted-phenoxide ion in transition state. Thus, it has been concluded that the reactions with the dissociated $EtO^-$ and ion-paired EtOK proceed through a stepwise mechanism, in which departure of the leaving group occurs after the RDS, and that $K^+$ ion catalyzes the reactions by increasing the electrophilicity of the reaction center through a four-membered cyclic TS structure.

• Bulletin of the Korean Chemical Society
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• 제33권9호
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• pp.2971-2975
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• 2012

Second-order rate constants $k_N$ have been measured spectrophotometrically for nucleophilic substitution reactions of t-butyl 4-pyridyl carbonate 8 with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 8 is linear with ${\beta}_{nuc}$ = 0.84. The ${\beta}_{nuc}$ value obtained for the reactions of 8 is much larger than that reported for the corresponding reactions of t-butyl 2-pyridyl carbonate 6 (i.e., ${\beta}_{nuc}$ = 0.44), which was proposed to proceed through a forced concerted mechanism. Thus, the aminolysis of 8 has been concluded to proceed through a stepwise mechanism with a zwitterionic tetrahedral intermediate $T^{\pm}$, in which expulsion of the leaving-group from $T^{\pm}$ occurs at the rate-determining step (RDS). In contrast, aminolysis of benzyl 4-pyridyl carbonate 7 has been reported to proceed through two intermediates, $T^{\pm}$ and its deprotonated form $T^-$ on the basis of the fact that the plots of pseudo-first-order rate constant $k_{obsd}$ vs. amine concentration curve upward. The current study has demonstrated convincingly that the nature of the leaving and nonleaving groups governs the reaction mechanism. The contrasting reaction mechanisms have been rationalized in terms of an intramolecular H-bonding interaction, steric acceleration, and steric inhibition.