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Bin Xu Shou‐Fei Zhu Xiao‐Dong Zuo Zhi‐Chao Zhang Qi‐Lin Zhou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(15):3994-3997
A highly enantioselective N H insertion reaction of α‐diazoketones was developed by using cooperative catalysis by dirhodium(II) carboxylates and chiral spiro phosphoric acids. The insertion reaction provides a new access route to diverse chiral α‐aminoketones, which are versatile building blocks in organic synthesis, with fast reaction rates, good yields and high enantioselectivity under mild and neutral conditions. 相似文献
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Protonation of a Biologically Relevant CuII μ‐Thiolate Complex: Ligand Dissociation or Formation of a Protonated CuI Disulfide Species? 下载免费PDF全文
Erica C. M. Ording‐Wenker Martijn van der Plas Dr. Maxime A. Siegler Dr. Célia Fonseca Guerra Prof. Dr. Elisabeth Bouwman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):16913-16921
The proton‐induced electron‐transfer reaction of a CuII μ‐thiolate complex to a CuI‐containing species has been investigated, both experimentally and computationally. The CuII μ‐thiolate complex [CuII2( LMeS )2]2+ is isolated with the new pyridyl‐containing ligand LMeSSLMe , which can form both CuII thiolate and CuI disulfide complexes, depending on the solvent. Both the CuII and the CuI complexes show reactivity upon addition of protons. The multivalent tetranuclear complex [CuI2CuII2( LS )2(CH3CN)6]4+ crystallizes after addition of two equivalents of strong acid to a solution containing the μ‐thiolate complex [CuII2( LS )2]2+ and is further analyzed in solution. This study shows that, upon addition of protons to the CuII thiolate compound, the ligand dissociates from the copper centers, in contrast to an earlier report describing redox isomerization to a CuI disulfide species that is protonated at the pyridyl moieties. Computational studies of the protonated CuII μ‐thiolate and CuI disulfide species with LSSL show that already upon addition of two equivalents of protons, ligand dissociation forming [CuI(CH3CN)4]+ and protonated ligand is energetically favored over conversion to a protonated CuI disulfide complex. 相似文献
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de Visser SP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(15):4533-4541
Density functional calculations on a mu-oxo-mu-peroxodiiron complex (1) with a tetrapodal ligand BPP (BPP=N,N-bis(2-pyridylmethyl)-3-aminopropionate) are presented that is a biomimetic of the active site region of ribonucleotide reductase (RNR). We have studied all low-lying electronic states and show that it has close-lying broken-shell singlet and undecaplet (S=0, 5) ground states with essentially two sextet spin iron atoms. In strongly distorted electronic systems in which the two iron atoms have different spin states, the peroxo group moves considerably out of the plane of the mu-oxodiiron group due to orbital rearrangements. The calculated absorption spectra of (1,11)1 are in good agreement with experimental studies on biomimetics and RNR enzyme systems. Moreover, vibrational shifts in the spectrum due to (18)O(2) substitution of the oxygen atoms in the peroxo group follow similar trends as experimental observations. To identify whether the mu-oxo-mu-1,2-peroxodiiron or the mu-oxo-mu-1,1-peroxodiiron complexes are able to epoxidize substrates, we studied the reactivity patterns versus propene. Generally, the reactions are stepwise via radical intermediates and proceed by two-state reactivity patterns on competing singlet and undecaplet spin state surfaces. However, both the mu-oxo-mu-1,2-peroxodiiron and mu-oxo-mu-1,1-peroxodiiron complex are sluggish oxidants with high epoxidation barriers. The epoxidation barriers for the mu-oxo-mu-1,1-peroxodiiron complex are significantly lower than the ones for the mu-oxo-mu-1,2-peroxodiiron complex but still are too high to be considered for catalytic properties. Thus, theory has ruled out two possible peroxodiiron catalysts as oxidants in RNR enzymes and biomimetics and the quest to find the actual oxidant in the enzyme mechanism continues. 相似文献
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Gen Zhang Yaohu Zhang Rui Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2011,123(44):10613-10616
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Mateusz Piontek Bernd Morgenstern Nils Steinbrück Bastian Oberhausen Guido Kickelbick Kaspar Hegetschweiler 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(6):678-685
Liu et al. [Chin. J. Struct. Chem. (1996). 15 , 371–373] reported the structure of 6‐hydroxy‐1,4‐diazepane di(hydrogen bromide), C5H12N2O·2HBr, which was interpreted in terms of neutral diazepane and HBr molecules. We found, however, ample evidence that the formation of an organic salt, consisting of a diammonium cation and two bromide anions, is more plausible. This interpretation is also in agreement with thermogravimetric analysis and with the observed solution behaviour. The crystal structure of 6‐hydroxy‐1,4‐diazepane‐1,4‐diium dibromide, C5H14N2O2+·2Br?, measured at 142 K, crystallized in the orthorhombic space group P212121. The structure displays O—H…Br and N—H…Br hydrogen bonding. Contact distances are given. A search in the Cambridge Structural Database for the singly‐bonded H—Br moiety revealed a total of 69 structures. The question, whether these structures really include HBr as neutral molecules or rather Br? anions and a protonated substrate such as an amine, is addressed. 相似文献
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Yumeng Xi Boliang Dong Edward J. McClain Qiaoyi Wang Tesia L. Gregg Novruz G. Akhmedov Jeffrey L. Petersen Xiaodong Shi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(18):4745-4749
A general method for the synthesis of α‐substituted vinyl sulfones makes use of a combination of a triazole gold complex and gallium triflate. This efficient C S bond formation between simple terminal alkynes and sulfinic acids provides access to various α‐substituted vinyl sulfones. 相似文献
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Xiu‐Lan Xie Shou‐Fei Zhu Jun‐Xia Guo Yan Cai Qi‐Lin Zhou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(11):3022-3025
A palladium‐catalyzed asymmetric O H insertion reaction was developed. Palladium complexes with chiral spiro bisoxazoline ligands promoted the insertion of α‐aryl‐α‐diazoacetates into the O H bond of phenols with high yield and excellent enantioselectivity under mild reaction conditions. This palladium‐catalyzed asymmetric O H insertion reaction provided an efficient and highly enantioselective method for the preparation of synthetically useful optically active α‐aryl‐α‐aryloxyacetates. 相似文献
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Da Zhao Jiji Zhang Zuowei Xie 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(47):13116-13120
o‐Carboryne can undergo α‐C H bond insertion with tertiary amines, thus affording α‐carboranylated amines in very good regioselectivity and isolated yields. In this process, the nucleophilic addition of tertiary amines to the multiple bond of o‐carboryne generates a zwitterionic intermediate. An intramolecular proton transfer, followed by a nucleophilic attack leads to the formation of the final product. Thus, regioselectivity is highly dependent upon the acidity of α‐C H proton of tertiary amines. This approach serves as an efficient methodology for the preparation of a series of 1‐aminoalkyl‐o‐carboranes. 相似文献
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Emma L. McInturff Khoa D. Nguyen Michael J. Krische 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(12):3296-3299
Direct ruthenium‐catalyzed C C coupling of alkynes and vicinal diols to form β,γ‐unsaturated ketones occurs with complete levels of regioselectivity and good to complete control over the alkene geometry. Exposure of the reaction products to substoichiometric quantities of p‐toluenesulfonic acid induces cyclodehydration to form tetrasubstituted furans. These alkyne‐diol hydrohydroxyalkylations contribute to a growing body of merged redox‐construction events that bypass the use of premetalated reagents and, hence, stoichiometric quantities of metallic by‐products. 相似文献