The enantioselective reduction of acetophenone analogues catalyzed by carrot and celeriac was performed in moderate conversions and excellent enantiomeric excesses.The steric factors and electronic effects of the subs...The enantioselective reduction of acetophenone analogues catalyzed by carrot and celeriac was performed in moderate conversions and excellent enantiomeric excesses.The steric factors and electronic effects of the substituents at the aromatic ring were found to significantly affect the efficiency of the enantioselective reduction of acetophenone analogues,while they had a little effect on the enantioselectivity of acetophenone analogues reduction.It was also found that the conversions of acetophenone analogu...展开更多
Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-1-phenyl-1-propanone with borane catalyzed by (S)-4-benzyl-5,5- diphenyl-1,3,2-oxazaborolidine at the B3LY...Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-1-phenyl-1-propanone with borane catalyzed by (S)-4-benzyl-5,5- diphenyl-1,3,2-oxazaborolidine at the B3LYP/6-31G* level. All molecular species involved in the four reaction steps have been fully optimized and the structural parameters are provided, and the micro process of reaction was also investigated. The catalyst-alkoxyborane adduct formed in step III exhibits a B-O-B-N tetra-atomic ring. Reaction coordination calculations show that BH3 can react with 3-morpholin-4-yl-1-phenyl-1-propanone spontaneously, resulting in the need of 2 mol BH3 in the reaction.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.
An operationally simple protocol was designed for the enantioselective silane reduction (ESR) of ketones using air- and moisture-stable [Ir(OMe)(cod)]<sub>2</sub> (cod = 1,5-cyclooctadiene) (3) as a metal ...An operationally simple protocol was designed for the enantioselective silane reduction (ESR) of ketones using air- and moisture-stable [Ir(OMe)(cod)]<sub>2</sub> (cod = 1,5-cyclooctadiene) (3) as a metal catalyst precursor. This reaction was driven by chiral hydroxyamide-functionalized azolium salt 2. The catalytic ESR reaction could be performed under benchtop conditions at room temperature. Treatment of 2 with 3 in THF yielded the monodentate IrCl(NHC)(cod) (NHC = N-heterocyclic carbene) complex 4 in 93% yield, herein the anionic methoxy ligand of 3 serves as an internal base that deprotonates the azolium ring of 2. The well-defined Ir complex 4 catalyzed the ESR reaction of propiophenone (6) with (EtO)<sub>2</sub>MeSiH using the pre-mixing reaction procedure. Based on this success, the catalytic ESR reaction was designed and implemented using an in situ-generated NHC/Ir catalyst derived from 2 and 3. Thus, a wide variety of aryl ketones could be reduced to the corresponding optically active alcohols in moderate to excellent stereoselectivities at room temperature without temperature control. Since the high catalytic activity of 3 was observed, we next evaluated several other transition metal catalyst precursors for the catalytic ESR reaction under the influence of 2. This evaluation revealed that Ir(acac)(cod) (acac = acetylacetonate) (28) and [IrCl(cod)]<sub>2</sub> (5) can be successfully used as metal catalyst precursors in the ESR reaction.展开更多
The asymmetric reduction of prochiral ketones was catalyzed by a class of recoverable and highly stable chiral ferrocenyl amino alcohols derived from natural amino acids to yield optically active secondary alcohols in...The asymmetric reduction of prochiral ketones was catalyzed by a class of recoverable and highly stable chiral ferrocenyl amino alcohols derived from natural amino acids to yield optically active secondary alcohols in high chemical yields and moderate to good enantiomeric excesses.展开更多
Theab 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 reduct...Theab 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 catalyst-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 to R-chiral alcohols.展开更多
The ab initio molecular orbital method is employed to study the enantioselective reduction of acetophenone with borane catalyzed by thiazolidinooxazaborolidine. Computation result shows that the controlling step for t...The ab initio molecular orbital method is employed to study the enantioselective reduction of acetophenone with borane catalyzed by thiazolidinooxazaborolidine. Computation result shows that the controlling step for the reduction is the decomposition of the catalyst-alkoxyborane adduct and the reduction leads to S-alcohols. The transition state of the hydride transfer from the borane moiety to the carbonyl carbon of acetophenone is a twisted chair structure with a B(2)-N(3)-B BH 3-H BH 3-C CO-O CO 6-membered ring.展开更多
An asymmetric borane reduction of prochiral ketones catalyzed by simple amino alcohols and corresponding amino acids was examined to give alcohols with e.e. value up to 92% .
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supported by the National Natural Science Foundation of China(No.20672037)the National Special Fund for State Key Laboratory of Bioreactor Engineering(No.2060204)
文摘The enantioselective reduction of acetophenone analogues catalyzed by carrot and celeriac was performed in moderate conversions and excellent enantiomeric excesses.The steric factors and electronic effects of the substituents at the aromatic ring were found to significantly affect the efficiency of the enantioselective reduction of acetophenone analogues,while they had a little effect on the enantioselectivity of acetophenone analogues reduction.It was also found that the conversions of acetophenone analogu...
基金Project supported by the Research Foundation of Suzhou University (Q3109306)
文摘Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-1-phenyl-1-propanone with borane catalyzed by (S)-4-benzyl-5,5- diphenyl-1,3,2-oxazaborolidine at the B3LYP/6-31G* level. All molecular species involved in the four reaction steps have been fully optimized and the structural parameters are provided, and the micro process of reaction was also investigated. The catalyst-alkoxyborane adduct formed in step III exhibits a B-O-B-N tetra-atomic ring. Reaction coordination calculations show that BH3 can react with 3-morpholin-4-yl-1-phenyl-1-propanone spontaneously, resulting in the need of 2 mol BH3 in the reaction.
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An operationally simple protocol was designed for the enantioselective silane reduction (ESR) of ketones using air- and moisture-stable [Ir(OMe)(cod)]<sub>2</sub> (cod = 1,5-cyclooctadiene) (3) as a metal catalyst precursor. This reaction was driven by chiral hydroxyamide-functionalized azolium salt 2. The catalytic ESR reaction could be performed under benchtop conditions at room temperature. Treatment of 2 with 3 in THF yielded the monodentate IrCl(NHC)(cod) (NHC = N-heterocyclic carbene) complex 4 in 93% yield, herein the anionic methoxy ligand of 3 serves as an internal base that deprotonates the azolium ring of 2. The well-defined Ir complex 4 catalyzed the ESR reaction of propiophenone (6) with (EtO)<sub>2</sub>MeSiH using the pre-mixing reaction procedure. Based on this success, the catalytic ESR reaction was designed and implemented using an in situ-generated NHC/Ir catalyst derived from 2 and 3. Thus, a wide variety of aryl ketones could be reduced to the corresponding optically active alcohols in moderate to excellent stereoselectivities at room temperature without temperature control. Since the high catalytic activity of 3 was observed, we next evaluated several other transition metal catalyst precursors for the catalytic ESR reaction under the influence of 2. This evaluation revealed that Ir(acac)(cod) (acac = acetylacetonate) (28) and [IrCl(cod)]<sub>2</sub> (5) can be successfully used as metal catalyst precursors in the ESR reaction.
文摘The asymmetric reduction of prochiral ketones was catalyzed by a class of recoverable and highly stable chiral ferrocenyl amino alcohols derived from natural amino acids to yield optically active secondary alcohols in high chemical yields and moderate to good enantiomeric excesses.
基金the Key Project of Science and Technology of the Ministry of Education, China.
文摘Theab 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 catalyst-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 to R-chiral alcohols.
基金ProjectsupportedbytheScienceFoundationofNationalEducationMinistry (No .9910 6 )
文摘The ab initio molecular orbital method is employed to study the enantioselective reduction of acetophenone with borane catalyzed by thiazolidinooxazaborolidine. Computation result shows that the controlling step for the reduction is the decomposition of the catalyst-alkoxyborane adduct and the reduction leads to S-alcohols. The transition state of the hydride transfer from the borane moiety to the carbonyl carbon of acetophenone is a twisted chair structure with a B(2)-N(3)-B BH 3-H BH 3-C CO-O CO 6-membered ring.
文摘An asymmetric borane reduction of prochiral ketones catalyzed by simple amino alcohols and corresponding amino acids was examined to give alcohols with e.e. value up to 92% .
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.
