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981.
Asymmetric Conjugate Alkynylation of Cyclic α,β‐Unsaturated Carbonyl Compounds with a Chiral Diene Rhodium Catalyst
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Dr. Xiaowei Dou Dr. Yinhua Huang Prof. Dr. Tamio Hayashi 《Angewandte Chemie (International ed. in English)》2016,55(3):1133-1137
Asymmetric conjugate alkynylation of cyclic α,β‐unsaturated carbonyl compounds (ketones, esters, and amides) was realized by use of diphenyl[(triisopropylsilyl)ethynyl]methanol as an alkynylating reagent in the presence of a rhodium catalyst coordinated with a new chiral diene ligand (Fc‐bod; bod=bicyclo[2.2.2]octa‐2,5‐diene, Fc=ferrocenyl) to give high yields of the corresponding β‐alkynyl‐substituted carbonyl compounds with 95–98 % ee. 相似文献
982.
Dr. Kazunobu Igawa Daisuke Yoshihiro Yusuke Abe Prof. Dr. Katsuhiko Tomooka 《Angewandte Chemie (International ed. in English)》2016,55(19):5814-5818
A variety of functionalized silacyclopentanes were synthesized by highly enantioselective β‐eliminations of silacyclopentene oxides followed by stereospecific transformations. The reaction mechanism of the β‐elimination was elucidated by DFT calculations. An in vitro biological assay with an oxy‐functionalized silacyclopentane showed substantial binding to a serotonin receptor protein. 相似文献
983.
Chiral Phosphoric Acid Catalyzed Asymmetric Ugi Reaction by Dynamic Kinetic Resolution of the Primary Multicomponent Adduct
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Yun Zhang Dr. Yu‐Fei Ao Prof. Dr. Zhi‐Tang Huang Prof. Dr. De‐Xian Wang Prof. Dr. Mei‐Xiang Wang Prof. Dr. Jieping Zhu 《Angewandte Chemie (International ed. in English)》2016,55(17):5282-5285
Reaction of isonitriles with 3‐(arylamino)isobenzofuran‐1(3H)‐ones in the presence of a catalytic amount of an octahydro (R)‐binol‐derived chiral phosphoric acid afforded 3‐oxo‐2‐arylisoindoline‐1‐carboxamides in high yields with good to high enantioselectivities. An enantioselective Ugi four‐center three‐component reaction of 2‐formylbenzoic acids, anilines, and isonitriles was subsequently developed for the synthesis of the same heterocycle. Mechanistic studies indicate that the enantioselectivity results from the dynamic kinetic resolution of the primary Ugi adduct, rather than from the C?C bond‐forming process. The resulting heterocycle products are of significant medicinal importance. 相似文献
984.
Dr. Matthieu Jouffroy Prof. Dr. Dominique Armspach Prof. Dr. Dominique Matt Prof. Dr. Kohtaro Osakada Dr. Daisuke Takeuchi 《Angewandte Chemie (International ed. in English)》2016,55(29):8367-8370
Cationic PdII monophosphine complexes derived from α‐ and β‐cyclodextrins (CDs) promote the homopolymerization of styrene under carbon monoxide pressure. Although reversible CO coordination takes place under catalytic conditions according to 13C NMR studies with 13C‐enriched CO, both complexes catalyze the formation of CO‐free styrene polymers. These macromolecules display optical activity as a result of the presence of stereoregular sequences within the overall atactic polymer. 相似文献
985.
Asymmetric Induction by a Nitrogen 14N/15N Isotopomer in Conjunction with Asymmetric Autocatalysis
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Dr. Arimasa Matsumoto Hanae Ozaki Shunya Harada Kyohei Tada Tomohiro Ayugase Hitomi Ozawa Prof. Dr. Tsuneomi Kawasaki Prof. Dr. Kenso Soai 《Angewandte Chemie (International ed. in English)》2016,55(49):15246-15249
Chirality arising from isotope substitution, especially with atoms heavier than the hydrogen isotopes, is usually not considered a source of chirality in a chemical reaction. An N2,N2,N3,N3‐tetramethyl‐2,3‐butanediamine containing nitrogen (14N/15N) isotope chirality was synthesized and it was revealed that this isotopically chiral diamine compound acts as a chiral initiator for asymmetric autocatalysis. 相似文献
986.
Stacking and Electrostatic Interactions Drive the Stereoselectivity of Silylium‐Ion Asymmetric Counteranion‐Directed Catalysis
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Trevor J. Seguin Prof. Steven E. Wheeler 《Angewandte Chemie (International ed. in English)》2016,55(51):15889-15893
Computational analysis shows that the enantioselectivity of asymmetric Lewis‐acid organocatalysis of the Diels–Alder cycloaddition of cyclopentadiene to cinnamates arises from stacking interactions that favor the addition of the diene to the more hindered face of the dienophile, while electrostatic interactions control the diastereoselectivity by selectively stabilizing the endo transition state. These results not only explain the stereoselectivity of these silylium‐ion‐ACDC reactions but should also guide the development of more effective ion‐pairing asymmetric organocatalysts. 相似文献
987.
988.
Enantioselective Access to Spirocyclic Sultams by Chiral Cpx–Rhodium(III)‐Catalyzed Annulations
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Manh V. Pham Prof. Dr. Nicolai Cramer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(7):2270-2273
Chiral spirocyclic sultams are a valuable compound class in organic and medicinal chemistry. A rapid entry to this structural motif involves a [3+2] annulation of an N‐sulfonyl ketimine and an alkyne. Although the directing‐group properties of the imino group for C?H activation have been exploited, the developments of related asymmetric variants have remained very challenging. The use of rhodium(III) complexes equipped with a suitable atropchiral cyclopentadienyl ligand, in conjunction with a carboxylic acid additive, enables an enantioselective and high yielding access to such spirocyclic sultams. 相似文献
989.
采用金属扩散管-芯片式高场非对称波形离子迁移谱(FAIMS)技术对苯丙氨酸进行了快速检测,设定测试压强为250 kPa,金属扩散管温度为190℃,在优化的最佳分析条件下,即:载气流速为2000 mL/min,分离电压为152.8 V时,在正模式下获得了苯丙氨酸的离子特征谱图和补偿电压特征值-0.62 V.另外,利用FAIMS对不同浓度的苯丙氨酸样品气进行了检测,确定了FAIMS检测的定量线性范围为6~20 mg/L和检出限为5.9 mg/L.本实验为FAIMS应用于苯丙氨酸的快速检测提供了重要参考. 相似文献
990.
Suresh Babu Meruva Raghavendra Rao K. Aaseef Mohammed Vilas H. Dahanukar U. K. Syam Kumar P. K. Dubey 《合成通讯》2016,46(2):187-196
A concise and enantioselective syntheses of antileukemic natural products such as (–)-(S)-goniothalamin and (–)-leiocarpin A has been accomplished in excellent yields. By employing reported conditions on suitable substrates via Julia–Kocienski olefination, intramolecular lactonization, and subsequently dehydroxylative olefination, (–)-(S)-goniothalamin was synthesized. Then Sharpless asymmetric dihydroxylation–intramolecular Michael addition on (–)-(S)-goniothalamin provided (–)-leiocarpin A. 相似文献