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Celia Blanco Dr. Joaquim Crusats Dr. Zoubir El‐Hachemi Prof. Albert Moyano Dr. David Hochberg Prof. Josep M. Ribó 《Chemphyschem》2013,14(11):2432-2440
The model of limited enantioselectivity (LES) in closed systems, and under experimental conditions able to achieve chemical equilibrium, can give rise to neither spontaneous mirror symmetry breaking (SMSB) nor kinetic chiral amplifications. However, it has been recently shown that it is able to lead to SMSB, as a stationary final state, in thermodynamic scenarios involving nonuniform temperature distributions and for compartmentalized separation between the two autocatalytic reactions. Herein, it is demonstrated how SMSB may occur in LES in a cyclic network with uniform temperature distribution if the reverse reaction of the nonenantioselective autocatalysis, which gives limited inhibition on the racemic mixture, is driven by an external reagent, that is, in conditions that keep the system out of chemical equilibrium. The exact stability analysis of the racemic and chiral final outcomes and the study of the reaction parameters leading to SMSB are resolved analytically. Numerical simulations, using chemical kinetics equations, show that SMSB may occur for chemically reasonable parameters. Numerical simulations on SMSB are also presented for speculative, but reasonable, scenarios implying reactions common in amino acid chemistry. 相似文献
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Celia Blanco Dr. Joaquim Crusats Dr. Zoubir El‐Hachemi Albert Moyano Dr. Sabino Veintemillas‐Verdaguer Dr. David Hochberg Prof. Josep M. Ribó 《Chemphyschem》2013,14(17):3982-3993
Simulations of a chemical kinetics model, based on the free‐energy relationships of classical primary nucleation theory, show that the deracemization phenomenon in systems of achiral or fast racemizing compounds yielding enantiopure crystals as the more stable solid phase is a true spontaneous mirror symmetry breaking process (SMSB). That is, the achievement of a stationary chiral state is more stable than the racemic one. The model translates the free‐energy relationships determined by the existence of a critical size cluster to a chemical kinetics model, in which the consideration of forward and backward reaction rate constants avoids the misuse of network parameters that violate thermodynamic constraints (microreversibility principle), which would lead to apparent in silico SMSB. The model provides qualitative agreement for deracemizations by mechanical attrition of visible crystals, as well as for those obtained under temperature gradients. The analysis of the effect of the system parameters to obtain a SMSB scenario shows that the network possesses the principal characteristics of SMSB networks: 1) an enantioselective autocatalytic stage, corresponding to the non‐linear kinetics of enantioselective (homochiral) cluster‐to‐cluster growth, and 2) the mutual inhibition step originating in the backward flow of chiral clusters towards smaller achiral clusters, or even to a racemizing monomer. The application of such a SMSB kinetic model to enantioselective polymerizations and to chiral biopolymers is discussed. 相似文献
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Self‐Replication and Amplification of Enantiomeric Excess of Chiral Multifunctionalized Large Molecules by Asymmetric Autocatalysis 下载免费PDF全文
Prof. Dr. Tsuneomi Kawasaki Mai Nakaoda Yutaro Takahashi Yusuke Kanto Nanako Kuruhara Kenji Hosoi Prof. Dr. Itaru Sato Arimasa Matsumoto Prof. Dr. Kenso Soai 《Angewandte Chemie (International ed. in English)》2014,53(42):11199-11202
Self‐replication of large chiral molecular architectures is one of the great challenges and interests in synthetic, systems, and prebiotic chemistry. Described herein is a new chemical system in which large chiral multifunctionalized molecules possess asymmetric autocatalytic self‐replicating and self‐improving abilities, that is, improvement of their enantioenrichment in addition to the diastereomeric ratio. The large chiral multifunctionalized molecules catalyze the production of themselves with the same structure, including the chirality of newly formed asymmetric carbon atoms, in the reaction of the corresponding achiral aldehydes and reagent. The chirality of the large multifunctionalized molecules controlled the enantioselectivity of the reaction in a highly selective manner to construct multiple asymmetric stereogenic centers in a single reaction. 相似文献
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Kawasaki T Okano Y Suzuki E Takano S Oji S Soai K 《Angewandte Chemie (International ed. in English)》2011,50(35):8131-8133
Trigger happy: Chiral oxygen isotopomers of hydrobenzoin ([(18) O](R)-1 and [(18) O](S)-1) acted as chiral triggers to induce the enantioselective addition of iPr(2) Zn to pyrimidine-5-carbaldehyde. An extremely small chiral influence arising from the presence of the oxygen isotope ((18) O) is amplified through asymmetric autocatalysis to enantioenrich the 5-pyrimidyl alkanol product. 相似文献
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Asymmetric Induction by a Nitrogen 14N/15N Isotopomer in Conjunction with Asymmetric Autocatalysis 下载免费PDF全文
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
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The discovery and development of asymmetric autocatalysis, in which the structures of the chiral catalyst and the chiral product are the same, are described. Chiral 5-pyrimidyl, 3-quinolyl, and 5-carbamoyl-3-pyridyl alkanols act as highly enantioselective asymmetric autocatalysts in the enantioselective addition of diisopropylzinc to the corresponding aldehydes, such as pyrimidine-5-carbaldehyde. 2-Alkynyl-5-pyrimidyl alkanol with an enantiomeric excess (ee) of >99.5% automultiplies practically perfectly as an asymmetric autocatalyst in a yield of >99% and >99.5% ee. Asymmetric autocatalysis with an amplification of ee has thus been realized. Consecutive asymmetric autocatalysis starting with chiral 2-alkynylpyrimidyl alkanol of only 0.6% ee amplifies its ee significantly, and yields itself as the product with >99.5% ee. The reaction of pyrimidine-5-carbaldehyde and diisopropylzinc in the presence of chiral initiators with low ee's, such as secondary alcohol, amine, carboxylic acid, mono-substituted [2.2]paracyclophane, and chiral primary alcohols due to deuterium substitution, regulates the absolute configuration of the resulting pyrimidyl alkanols, and the ee of the resulting pyrimidyl alkanol is much higher than that of the chiral initiator. Leucine and [6]helicene with very low ee's, which are known to be induced by circularly polarized light (CPL), also serve as chiral initiators to produce pyrimidyl alkanol with higher ee's. Overall, the process represents the first correlation between the chirality of CPL and an organic compound with very high ee. Chiral inorganic crystals, such as quartz and sodium chlorate, act as chiral inducers in the asymmetric autocatalysis of pyrimidyl alkanol. The process correlates for the first time ever the chirality of inorganic crystals with an organic compound with very high ee. 相似文献
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Cover Picture: Asymmetric Induction by a Nitrogen 14N/15N Isotopomer in Conjunction with Asymmetric Autocatalysis (Angew. Chem. Int. Ed. 49/2016) 下载免费PDF全文
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):15183-15183
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Mark Busch Martin Schlageter Daniel Weingand Timo Gehring Dipl.‐Chem. Dipl.‐Math. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(33):8251-8258
Herein, we present a new substrate for the Soai reaction, which has an adamantylethynyl residue ( 1 g ) and exhibits asymmetric autocatalysis, yielding products with enantiomeric excesses above 99 %. For the first time, all reactions were performed on a parallel synthesizer system to ensure identical reaction conditions. A detailed systematic study of reaction parameters was performed and we report the highest enhancements of enantiomeric excess reported so far in the Soai reaction in one reaction cycle (7.2→94.1 % ee or 3.1→92.1 % ee). Our results led to a set of reaction parameters that yield reproducible results. Therefore, our new starting material 1 g is suitable for systematic and mechanistic studies on this remarkable reaction. A series of experiments designed to quantify the amplification of enantiomeric excess demonstrated that the reaction can be used in principle as a tool for the detection of low enantiomeric excesses: under definite conditions, an unknown low enantiomeric excess (0.1–7 %) was amplified to a detectable one. A back calculation to the original value offers a new method for the determination of small enantiomeric excesses. 相似文献
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《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):30-37
The exploitation of the asymmetry at silicon in stereoselective synthesis is an exceptionally challenging task. Initially, silicon‐stereogenic silanes have been utilized to elucidate the stereochemical course of substitution reactions at silicon. Apart from these mechanistic investigations, only a handful of synthetic applications with an asymmetrically substituted silicon as the stereochemical controller have been reported to date. In these transformations the chiral silicon functions as a chiral auxiliary. Conversely, a direct transfer of chirality from silicon to carbon during bond formation and cleavage at silicon has remained open until its recent realization in both inter‐ and intramolecular reactions. In this Concept, the pivotal considerations in relation to the nature of suitable silanes as well as mechanistic prerequisites for an efficient chirality transfer will be discussed. 相似文献