Two new type of 1,3,2-oxazaborolidines were prepared from (Is,2s)-2-amino-1-(4-nitrophenyl)-propane-1-3-diol and were used as catalyst in the asymmetric reduction of acetophenone. The influence of the reaction tempera...Two new type of 1,3,2-oxazaborolidines were prepared from (Is,2s)-2-amino-1-(4-nitrophenyl)-propane-1-3-diol and were used as catalyst in the asymmetric reduction of acetophenone. The influence of the reaction temperature as well as the effect of the structure of catalyst on the enantioselectivity was investigated. The origin of the products' configuration was discussed.展开更多
Two new chiral oxazaborolidine derivated from L-cystine have been used to catalyze the enantioselective reduction of prochiral ketones and the secondary alcohols are obtained with good to excellent opitical yields.
The enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine is discussed by the density functional theory (DFT) method. The main intermediates and transition states for this reaction ar...The enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine is discussed by the density functional theory (DFT) method. The main intermediates and transition states for this reaction are optimized completely at the B3LYP/6-31g(d) level, and the transition states are verified by vibrational modes. As shown, the chirality-controlled steps for this re- action are the hydride transfer from borane to carbonyl carbon and oxime carbon of keto oxime ether, and the chirality for the reduced products is determined in these two reaction steps. In all examined reaction paths, the first hydride is transferred via a six-membered ring and the second hydride via a five-membered ring or a four-membered ring.展开更多
The ab initio molecular orbital study on the mechanism of enantioselective reduction of 3,3-dimethyl butanone-2 with borane catalyzed by chiral oxazaborolidine is performed. As illustrated, this enantioselective reduc...The ab initio molecular orbital study on the mechanism of enantioselective reduction of 3,3-dimethyl butanone-2 with borane catalyzed by chiral oxazaborolidine is performed. As illustrated, this enantioselective reduction is exothermic and goes mainly through the formations of the catalyst-borane adduct, the catalyst-borane-3,3-dimethyl butanone-2 adduct, and the cata-lyst-alkoxyborane adduct with a B-O-B-N 4-member ring and through the decomposition of the catalyst-alkoxyborane adduct with the regeneration of the catalyst. During the hydride transfer in the catalyst-borane-3,3-dimethyl butanone-2 adduct to form the catalyst-alkoxyborane adduct, the hydride transfer and the formation of the B-O-B-N 4-member ring in the catalyst-alkoxyborane adduct happen simultaneously. The controlling step for the reduction is the transfer of hydride from the borane moiety to the carbonyl carbon of 3,3-dimethyl butanone-2. The transition state for the hydride transfer is a twisted chair structure and the reduction leads展开更多
The quantum chemical method is employed to study the enantioselective reduction of imine with borane catalyzed by chiral oxazaborolidine. All the structures are optimized completely at the B3LYP/6-31G(d) level. The ca...The quantum chemical method is employed to study the enantioselective reduction of imine with borane catalyzed by chiral oxazaborolidine. All the structures are optimized completely at the B3LYP/6-31G(d) level. The catalysis property of oxazaborolidine is notable. The reduction goes mainly through the formations of the catalyst-borane adduct, the catalyst-borane-imine adduct, and the catalyst-amidoborane adduct and the dissociation of the catalyst-amidoborane adduct with the regeneration of the catalyst. The controlling step for the reduction is the dissociation of the catalyst-amidoborane adduct. The main reduced product predicted theoretically is (R )-sec- ondary amine, which is in agreement with the experiment.展开更多
A new series of 1,3,2-oxazaborolidine catalysts substituted in position 4 by the (CH3)(3)C(CH2)(n) group (n=2, 3, 4, 5) were synthesized and applied to the borane reduction of prochiral ketones. The relationship betwe...A new series of 1,3,2-oxazaborolidine catalysts substituted in position 4 by the (CH3)(3)C(CH2)(n) group (n=2, 3, 4, 5) were synthesized and applied to the borane reduction of prochiral ketones. The relationship between catalyst structure and enantioselectivity was discussed.展开更多
基金This work was supported by, the NNSFC.!(29972012)
文摘Two new type of 1,3,2-oxazaborolidines were prepared from (Is,2s)-2-amino-1-(4-nitrophenyl)-propane-1-3-diol and were used as catalyst in the asymmetric reduction of acetophenone. The influence of the reaction temperature as well as the effect of the structure of catalyst on the enantioselectivity was investigated. The origin of the products' configuration was discussed.
文摘Two new chiral oxazaborolidine derivated from L-cystine have been used to catalyze the enantioselective reduction of prochiral ketones and the secondary alcohols are obtained with good to excellent opitical yields.
文摘The enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine is discussed by the density functional theory (DFT) method. The main intermediates and transition states for this reaction are optimized completely at the B3LYP/6-31g(d) level, and the transition states are verified by vibrational modes. As shown, the chirality-controlled steps for this re- action are the hydride transfer from borane to carbonyl carbon and oxime carbon of keto oxime ether, and the chirality for the reduced products is determined in these two reaction steps. In all examined reaction paths, the first hydride is transferred via a six-membered ring and the second hydride via a five-membered ring or a four-membered ring.
基金the Key Project of Science and Technology of the Ministry of Education, China.
文摘The ab initio molecular orbital study on the mechanism of enantioselective reduction of 3,3-dimethyl butanone-2 with borane catalyzed by chiral oxazaborolidine is performed. As illustrated, this enantioselective reduction is exothermic and goes mainly through the formations of the catalyst-borane adduct, the catalyst-borane-3,3-dimethyl butanone-2 adduct, and the cata-lyst-alkoxyborane adduct with a B-O-B-N 4-member ring and through the decomposition of the catalyst-alkoxyborane adduct with the regeneration of the catalyst. During the hydride transfer in the catalyst-borane-3,3-dimethyl butanone-2 adduct to form the catalyst-alkoxyborane adduct, the hydride transfer and the formation of the B-O-B-N 4-member ring in the catalyst-alkoxyborane adduct happen simultaneously. The controlling step for the reduction is the transfer of hydride from the borane moiety to the carbonyl carbon of 3,3-dimethyl butanone-2. The transition state for the hydride transfer is a twisted chair structure and the reduction leads
文摘The quantum chemical method is employed to study the enantioselective reduction of imine with borane catalyzed by chiral oxazaborolidine. All the structures are optimized completely at the B3LYP/6-31G(d) level. The catalysis property of oxazaborolidine is notable. The reduction goes mainly through the formations of the catalyst-borane adduct, the catalyst-borane-imine adduct, and the catalyst-amidoborane adduct and the dissociation of the catalyst-amidoborane adduct with the regeneration of the catalyst. The controlling step for the reduction is the dissociation of the catalyst-amidoborane adduct. The main reduced product predicted theoretically is (R )-sec- ondary amine, which is in agreement with the experiment.
基金Project supported by the National Natural Science Foundation of China and the Natural Science Foundation of Jiangsu Education Commission of China
文摘A new series of 1,3,2-oxazaborolidine catalysts substituted in position 4 by the (CH3)(3)C(CH2)(n) group (n=2, 3, 4, 5) were synthesized and applied to the borane reduction of prochiral ketones. The relationship between catalyst structure and enantioselectivity was discussed.
