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Tomohito Morosaki Tsubasa Suzuki Wei‐Wei Wang Shigeru Nagase Takayoshi Fujii 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(36):9723-9725
Electronic effects on the central carbon atom of carbone, generated by the replacement of the SIV ligand of carbodisulfane (CDS) with other chalcogen ligands (Ph2E, E=S or Se), were investigated. The carbones Ph2E→C←SPh2(NMe) [E=S( 1 ) or Se( 2 )] were synthesized from the corresponding salts, and their molecular structures and electronic properties were characterized. The carbone 2 is the first carbone containing selenium as the coordinated atom. DFT calculations revealed the electronic structures of 1 and 2 , which have two lone pairs of electrons at the carbon center. The trend in HOMO energy levels, estimated by cyclic voltammetry measurements, for the carbones and CDS follows the order of 2 > 1 >CDS. Analysis of a doubly protonated dication and trication complex revealed that the central carbon atom of 2 behaves as a four‐electron donor. 相似文献
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Catalytic Enantioselective Reaction of α‐Phenylthioacetonitriles with Imines Using Chiral Bis(imidazoline)–Palladium Catalysts 下载免费PDF全文
Masaru Kondo Natsumi Kobayashi Prof. Dr. Tsubasa Hatanaka Prof. Dr. Yasuhiro Funahashi Prof. Dr. Shuichi Nakamura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9066-9070
The catalytic enantioselective reaction of α‐phenylthioacetonitriles with imines has been developed. The reaction of various imines proceeds in good yields and diastereo‐ and enantioselectivities in the presence of chiral bis(imidazoline)–palladium catalysts. The obtained products can be converted into β‐aminonitrile or β‐aminoamide compounds without loss of enantiopurity. 相似文献
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The intramolecular Pauson–Khand cyclization in the presence of both aniline and nitrobenzene was used to improve the construction of N-nitrobenzenesulfonyl-protected 3-azabicyclo[4.3.0]nonane skeletons. We found that aniline enhanced the cyclization and that nitrobenzene prevents the concurrent reduction in this process. This combination of mediators allows for the efficient synthesis of bioactive azabicyclic nonane-type alkaloids and the use of milder deprotection conditions in the synthetic route. 相似文献
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Thermal [2+2] cycloaddition of morpholinoenamines with C60 via a single electron transfer 总被引:1,自引:0,他引:1
The thermal reaction of C(60) with five- and six-membered morpholinocycloalkenes in refluxing toluene exclusively gave the [2+2] cycloadducts in high yields. However, a seven-membered homologue sluggishly reacted with C(60) because of the increasing steric hindrance. This cycloaddition reaction is likely to proceed via a single electron transfer (SET), a radical-coupling, and subsequent ion cyclization rather than the prior proton transfer between the radical ions. 相似文献
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Highly enantioselective gem-chlorofluorination of active methylene compounds was carried out by using a copper(II) complex of a chiral spiro pyridyl monooxazoline ligand. This reaction yielded α-chloro-α-fluoro-β-keto esters and α-chloro-α-fluoro-β-keto phosphonates with up to 92% ee. The resulting dihalo β-keto ester was converted into various α-fluoro-α-heteroatom-substituted carbonyl compounds via nucleophilic substitution without loss of optical purity. A fully protected β-amino acid with a gem-chlorofluoromethylene function was also synthesized. 相似文献
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Dr. Tsubasa Nakashima Haruka Fujimori Dr. Kohsuke Ohmatsu Prof. Takashi Ooi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(36):9253-9256
Intermediary radical cations, generated through single-electron oxidation of enol silyl ethers by excited Ir-based photocatalysts, can be exploited as Brønsted acids for the activation of heteroarylcyanides. This strategy enables the direct allylic C−H heteroarylation of enol silyl ethers under visible-light irradiation. 相似文献
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We study the possibility of testing local realistic theory (LRT) based on the Bell inequality for the correlations in the decay modes of entangled K or B-mesons. It is shown that such a test is possible for a restricted class of LRT, despite the passive nature of decay events and/or the non-unitary treatment of the correlations which invalidate the test for general LRT. Unfortunately, the present setup of the KEKB (Belle) experiment, where the coherence of entangled B-mesons has been confirmed recently, does not admit such a test due to the indeterminacy in the separate decay times of the entangled pairs. 相似文献
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