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121.
An efficient asymmetric synthesis of selective estrogen receptor β-modulator (S)-4-bromo-9a-butyl-8-chloro-6-fluoro-7-hydroxy-1,2,9,9a-tetrahydro-fluoren-3-one was developed. The route features a chemoselective aromatic chlorination reaction, an asymmetric phase-transfer-catalyzed alkylation of an indanone with efficient ee upgrade by racemate crystallization, and a robust bromination reaction using imidazole as an in situ bromine trap to avoid overreaction. The synthesis proceeds in 34% yield over 8 steps from 2-fluoroanisole, and provides material with >99.5% ee. 相似文献
122.
Stereoselective conjugate additions to chiral N-enoyl amides employing various monoorganocuprate reagents, Li[RCuI], are described. The presence of TMSI in the addition of Li[RCuI] in THF provided the highest stereoselectivities. Reversed major diastereomeric ratios were obtained employing Li[RCuI] in ether or conventional copper-promoted Grignard reagents. The results presented support the favored anti-s-cis conformation of the substrates using Li[RCuI]/TMSI in THF, while the copper-promoted Grignard reagents or the Li[RCuI] reagents in ether favor the opposite syn-s-cis conformation. Influence of lithium ions on the stereoselective conjugate addition of the monoorganocuprate reagent, Li[BuCuI], has been investigated and two different mechanistic pathways are presented. The results show that iodotrimethylsilane (TMSI) is crucial for the asymmetric conjugate addition of the copper reagent, but only in THF or when 12-crown-4 is used. The reaction is thought not to involve any halosilane in any critical steps in the organocopper mechanisms conducted in ether. The (CuI)4(SMe2)3 complex precursor plays an instrumental role for the conjugate addition using monoorganocopper reagents. 相似文献
123.
A variety of optically active carboxylic esters are produced by the kinetic resolution of racemic secondary benzylic alcohols using free carboxylic acids with benzoic anhydride and tetramisole derivatives. 4-Methoxybenzoic anhydride (PMBA) is the best reagent to use in producing the corresponding esters in high ee when the reaction is catalyzed by (+)-benzotetramisole (BTM); by contrast, when non-substituted benzoic anhydride is used as a coupling reagent, the resulting optically active alcohols are obtained with high selectivities. This protocol directly produces chiral carboxylic esters from free carboxylic acids and racemic secondary alcohols by utilizing the trans-acylation process to generate mixed anhydrides from acid components and benzoic anhydride derivatives under the influence of chiral catalysts. 相似文献
124.
Tomoyuki Manaka Shin‐Ichiro Nagayama Wannaporn Desadee Naoki Yajima Takuya Kumamoto Toshiko Watanabe Tsutomu Ishikawa Masatoshi Kawahata Kentaro Yamaguchi 《Helvetica chimica acta》2007,90(1):128-142
Nucleophilic ring‐opening reactions of 3‐aryl‐1‐benzylaziridine‐2‐carboxylates were examined by using O‐nucleophiles and aromatic C‐nucleophiles. The stereospecificity was found to depend on substrates and conditions used. Configuration inversion at C(3) was observed with O‐nucleophiles as a major reaction path in the ring‐opening reactions of aziridines carrying an electron‐poor aromatic moiety, whereas mixtures containing preferentially the syn‐diastereoisomer were generally obtained when electron‐rich aziridines were used (Tables 1–3). In the reactions of electron‐rich aziridines with C‐nucleophiles, SN2 reactions yielding anti‐type products were observed (Table 4). Reductive ring‐opening reaction by catalytic hydrogenation of (+)‐trans‐(2S,3R)‐3‐(1,3‐benzodioxol‐5‐yl)aziridine‐2‐carboxylate (+)‐trans‐ 3c afforded the corresponding α‐amino acid derivative, which was smoothly transformed into (+)‐tert‐butyl [(1R)‐2‐(1,3‐benzodioxol‐5‐yl)‐1‐methylethyl]carbamate((+)‐ 14 ) with high retention of optical purity (Scheme 6). 相似文献
125.
Shimpei Sugiyama 《Tetrahedron letters》2005,46(39):6771-6775
Treatment of optically active 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from symmetrical ketones and (R)-(−)-chloromethyl p-tolyl sulfoxide in three steps, with lithium enolate of carboxylic acid tert-butyl esters gave optically active adducts having a substituent at the α-position with high 1,4-chiral induction from the sulfur chiral center in high yields. The adducts were converted to optically active esters and carboxylic acids having a chiral center at the α-position. When this addition reaction was carried out with the ester enolate generated from excess carboxylic acid tert-butyl ester with LDA in the presence of HMPA, the diastereomer of the adduct was obtained. By using the two reaction conditions for the generation of the ester enolates, a new method for asymmetric synthesis of both enantiomers of carboxylic acid derivatives having a substituent at the α-position from the one chiral source, (R)-(−)-chloromethyl p-tolyl sulfoxide, was realized. 相似文献
126.
The catalyst comprised [PdCl(η3-C3H5)]2 and a simple chiral hemilabile ferrocene ligand, 1′,2-bis(diphenylphosphinoethyl)ferrocenyl alcohol, provides synthetically acceptable results for an enantioselective Pd-catalyzed allylic alkylation of cyclohexanone derivatives bearing an electron-withdrawing group at the α-position to form the quaternary carbon with up to 90% enantioselectivity under mild reaction conditions. 相似文献
127.
(E)/(Z)-Isomeric allylic carbamate esters were deprotonated by n-butyllithium/(−)-sparteine in toluene. Trapping experiments with chlorotrimethylsilane afforded the α-substitution products, with (R)-configuration, revealing that the pro-S proton is removed predominantly to form the corresponding (S)-lithium·(−)-sparteine derivatives; kS/kR>15:1 and >7:1, respectively. A slow (S)→(R)-epimerization occurs at −78 °C (T1/2>60 min). The allylic double bond is stable to (Z)-(E) isomerization under these conditions. 相似文献
128.
Many polymeric membranes are produced by phase inversion technique invented by Loeb and Sourirajan in 1962. The dry-casting method is one of the major phase inversion techniques in which a homogeneous polymer solution consisting of solvent(s) and nonsolvent(s) is cast on a support and then evaporation of the casting solution takes place under convective conditions. In this paper, we model membrane formation by the dry-casting method. The model takes into account film shrinkage, evaporative cooling, coupled heat, and mass transfer and incorporates practical and reliable diffusion theory as well as complex boundary conditions especially at the polymer solution/air interface. The predictions from the model provide composition paths, temperature, and thickness of the solution. By plotting the composition paths on the ternary phase diagram, we ascertain the general structural characteristics of the membranes prepared from particular casting conditions. The predictive ability of the model was evaluated by comparing the results with the experimental data obtained from gravimetric measurements for cellulose acetate (CA)–acetone–water system. In an attempt to illustrate the importance of diffusion formalism on the predictions, recently proposed multicomponent diffusion theory and its simplified forms were utilized in the model. The computational results show that the critical factor for capturing the accurate behavior of membrane formation is the diffusion formalism utilized in the model. 相似文献
129.
An asymmetric hydrogenation of aroylacrylic acids catalyzed by RuPHOX-Ru catalyst has been developed, affording the corresponding chiral γ-lactones in high yields and with up to 93% ee. The methodology has the advantage of utilizing easily accessible substrates and has therefore expand the scope of the resulting chiral γ-lactones. Furthermore, high catalytic efficiency was achieved in that the reduction of both the CC and CO double bonds was achieved in one step. The current work provides an alternative and convenient pathway for the synthesis of a wide range of chiral γ-lactones. 相似文献
130.
Hui Wang 《Tetrahedron letters》2005,46(6):963-966
Well-defined Ru amido complexes effected asymmetric Michael addition of β-keto esters to 2-cyclopenten-1-one to give quantitatively the corresponding Michael adducts with excellent ee although with a 1:1 diastereomer ratio. The stereochemical outcome of the reaction was significantly influenced by the structures of the catalysts and the structures of the β-keto esters; the ee value reaching up to 97%. 相似文献