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排序方式: 共有485条查询结果,搜索用时 187 毫秒
91.
Dr. Pandur Venkatesan Balaji Dr. Zhao Li Dr. Akira Saito Dr. Naoya Kumagai Prof. Dr. Masakatsu Shibasaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15524-15527
A fluorine-containing tetrasubstituted stereogenic center is a highly valued structural feature in medicinal chemistry. Herein, we describe the direct coupling of racemic α-fluoronitriles and aldehydes promoted by a chiral CuI/Barton's base catalytic system, delivering α-tetrasubstituted α-fluoro-β-hydroxynitriles with satisfactory stereoselection. The stereochemical course was positively biased by the combined use of asymmetrical achiral thiourea as a supplementary ligand for CuI, which significantly enhanced the stereoselectivity. Both aromatic and aliphatic aldehydes were implemented to provide densely and stereoselectively functionalized chiral building blocks with aliphatic and aromatic tails. 相似文献
92.
A bicyclic dipeptide derivative with fixed conformation simulating that of the two central amino acid residues in type II′ β-turn has been synthesized starting from L-glutamic acid and L-cysteine in short steps. 相似文献
93.
The vinyloxyborane(5), prepared from (+)--phenyl-3()-butanethioate, 9-BBN triflate and diisopropylethylamine, reacted with -(3-benzyloxypropylidene)benzylamine to give the β-benzylamino thiol ester(6) in a moderate yield, which was efficiently converted to the optically pure thienamycin intermediate(10). 相似文献
94.
95.
Yamagiwa N Tian J Matsunaga S Shibasaki M 《Journal of the American Chemical Society》2005,127(10):3413-3422
Full details of a catalytic asymmetric cyano-ethoxycarbonylation reaction promoted by a heterobimetallic YLi3 tris(binaphthoxide) complex (YLB 1), especially mechanistic studies, are described. In the cyanation reaction of aldehydes with ethyl cyanoformate, three achiral additives, H2O, tris(2,6-dimethoxyphenyl)phosphine oxide (3a), and BuLi, were required to achieve high reactivity and enantioselectivity (up to >99% yield and up to 98% ee). The roles of achiral additives and the reaction pathway were investigated in detail. In situ IR analysis revealed that the initiation step to generate LiCN from H2O, BuLi, and ethyl cyanoformate is rather slow. On the basis of mechanistic studies of the initiation step to generate an active nucleophilic species, reaction conditions were optimized by using a catalytic amount of acetone cyanohydrin as an initiator. Under the optimized conditions, the induction period decreased and the reaction completed within 9 min using 5 mol % YLB at -78 degrees C. Catalyst loading was successfully reduced to 1 mol %. Kinetic experiments and evaluation of the substituent effects of phosphine oxide revealed that phosphine oxide had beneficial effects on both the reaction rate and the enantioselectivity. The putative active species as well as the catalytic cycle of the reaction are also discussed. 相似文献
96.
Yuichiro Tada Masakatsu Ueno Noriaki Tsuchihashi Kiyoshi Shimizu 《Journal of solution chemistry》1994,23(9):973-987
The limiting molar conductances ° of potassium deuteroxide KOD in D2O and potassium hydroxide KOH in H2O were determined at 5 and 45°C as a function of pressure to clarify the difference in the temperature, pressure and isotope effects on the proton jump between an OD– (OH–) and a D3O+ (H3O+) ion. The excess conductances of the OD– ion in D2O and the OH– ion in H2O,
E
0
(OD-) and
E
0
(OH-), increase with increasing temperature and pressure as in the case of the excess deuteron and proton conductances,
E
0
(D+) and
E
0
(H+). However, the temperature effect on the excess conductance is larger for the OD–(OH–) ion than for the D3O+ (H3O+) ion but the pressure effect is much smaller for the OD– (OH–) ion than for the D3O+ (H3O+) ion. These findings are correlated with larger activation energies and less negative activation volumes found for the OD– (OH–) ion than for the D3O+ (H3O+) ion. Concerning the isotope effect, the value of
E
0
(OH-)/
E
0
(OD-) deviates considerably from
at each temperature and pressure in contrast with that of
E
0
(H+)/
E
0
(D+), although both of them decrease with increasing temperature and pressure. These results are discussed mainly in terms of the difference in repulsive force between the OD– (OH–) or the D3O+ (H3O+) ion and the adjacent water molecule, the difference in strength of hydrogen bonds in D2O and H2O, and their variations with temperature, pressure, and isotope. 相似文献
97.
98.
A highly congested bicyclo[3.3.1]nonanone core of polycyclic polyprenylated acylphloroglucinols was constructed using a stereoselective Claisen rearrangement and an intramolecular aldol reaction as the key steps. The stereochemistry of C-4 appeared to control the ground state conformation of the cyclohexenone core, which determined the diastereoselectivity in the Claisen rearrangement. 相似文献
99.
Lactacystin and salinosporamide A are fascinating molecules with regard to both their chemical structures and biological activities. These naturally occurring compounds are potent and selective proteasome inhibitors. The molecular structures are characterized by their densely functionalized γ‐lactam cores. The structure and biological properties of these two compounds are attracting the attention of many chemists as challenging synthetic targets. We discuss their synthetic strategies in this review. 相似文献
100.
Hongbo Qin Noriyuki Yamagiwa Dr. Shigeki Matsunaga Dr. Masakatsu Shibasaki Prof. Dr. 《化学:亚洲杂志》2007,2(1):150-154
Catalytic intermolecular hydroamination of vinyl arenes is described. Our initial investigation revealed that a Bi(OTf)3/[Cu(CH3CN)4]PF6 system previously developed for catalytic intermolecular hydroamination of 1,3‐dienes was suitable for hydroamination of a styrene with sulfonamides, but the substrate generality of this system was unsatisfactory. Several metals were screened to expand the substrate scope, and a new Hf(OTf)4/[Cu(CH3CN)4]PF6 system was determined to be highly suitable. The combination of Hf(OTf)4 and [Cu(CH3CN)4]PF6 efficiently promoted the hydroamination of various vinyl arenes, including less‐reactive vinyl arenes with electron‐withdrawing groups. This strategy was applied to sulfonamides, carbamates, and carboxamides, and products were obtained in up to 99 % yield with 0.3–10 mol % catalyst loading. 相似文献