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61.
Fused Perylene–Phthalocyanine Macrocycles: A New Family of NIR‐Dyes with Pronounced Basicity 下载免费PDF全文
Jörg Schönamsgruber Dr. Harald Maid Prof. Dr. Walter Bauer Prof. Dr. Andreas Hirsch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):16969-16979
The synthesis and characterization of a new type of chromophore, namely PePc consisting of a central phthalocyanine core and four fused perylene–bisimide (PBI) units is described for the first time. The entire architecture represents a highly extended conjugated heterocyclic π‐system with C4h symmetry. In order to guarantee pronounced solubility in organic solvents the corresponding PBI units were bay‐functionalized with tert‐butylphenoxy substituents. Next to the metal‐free macrocycle, PePcH2, also metallated macrocycles PePcM (M=Zn, Ni, Pb, Ru, Fe) were synthesized. The extensive fusion of the corresponding aromatic building blocks to the very large extended π‐system leads to a very narrow HOMO–LUMO gap and as a consequence to transparency in the visible but light absorption in the NIR region. Significantly, the azomethine N‐atoms N1?N4 of PePcM and PePcH2 are highly basic. The corresponding tetraprotonated systems can only be deprotonated with very strong non‐nucleophilic bases such as phosphazene bases. In the protonated forms PePcMH44+ and PePcMH64+ the absorption maximum is shifted back to the visible region due to the loss of conjugation. The experimental findings were corroborated with quantum mechanical calculations. 相似文献
62.
Inside Back Cover: Size‐Selective Complexation and Extraction of Endohedral Metallofullerenes with Cycloparaphenylene (Angew. Chem. Int. Ed. 12/2014) 下载免费PDF全文
63.
Total Synthesis of the Antibiotic Kendomycin: A Macrocyclization Using the Tsuji–Trost Etherification 下载免费PDF全文
Dr. Tetsuya Sengoku Dr. Shu Xu Kenji Ogura Yoshinori Emori Kenji Kitada Prof. Dr. Daisuke Uemura Prof. Dr. Hirokazu Arimoto 《Angewandte Chemie (International ed. in English)》2014,53(16):4213-4216
A highly stereocontrolled, convergent total synthesis of kendomycin [(?)‐TAN2162], an ansa‐macrocyclic antibiotic, is reported. The key of the strategy is an unprecedented Tsuji–Trost macrocyclic etherification, followed by a transannular Claisen rearrangement to construct the 18‐membered carbocyclic framework. The oxa‐six‐ and five‐membered rings were also stereoselectively constructed respectively by a cascade oxidative cyclization at an unfunctionalized benzylic position and using a one‐pot epoxidation/5‐exo‐tet epoxide opening. 相似文献
64.
Dr. Timothy A. Hill Dr. Nicholas E. Shepherd Dr. Frederik Diness Prof. Dr. David P. Fairlie 《Angewandte Chemie (International ed. in English)》2014,53(48):13020-13041
Many proteins exert their biological activities through small exposed surface regions called epitopes that are folded peptides of well‐defined three‐dimensional structures. Short synthetic peptide sequences corresponding to these bioactive protein surfaces do not form thermodynamically stable protein‐like structures in water. However, short peptides can be induced to fold into protein‐like bioactive conformations (strands, helices, turns) by cyclization, in conjunction with the use of other molecular constraints, that helps to fine‐tune three‐dimensional structure. Such constrained cyclic peptides can have protein‐like biological activities and potencies, enabling their uses as biological probes and leads to therapeutics, diagnostics and vaccines. This Review highlights examples of cyclic peptides that mimic three‐dimensional structures of strand, turn or helical segments of peptides and proteins, and identifies some additional restraints incorporated into natural product cyclic peptides and synthetic macrocyclic peptidomimetics that refine peptide structure and confer biological properties. 相似文献
65.
Dr. Krystle C. H. Chua Dr. Markus Pietsch Xiaozhou Zhang Stephanie Hautmann Hon Y. Chan Dr. John B. Bruning Prof. Dr. Michael Gütschow Prof. Dr. Andrew D. Abell 《Angewandte Chemie (International ed. in English)》2014,53(30):7828-7831
There is a real need for simple structures that define a β‐strand conformation, a secondary structure that is central to peptide–protein interactions. For example, protease substrates and inhibitors almost universally adopt this geometry on active site binding. A planar pyrrole is used to replace two amino acids of a peptide backbone to generate a simple macrocycle that retains the required geometry for active site binding. The resulting β‐strand templates have reduced peptide character and provide potent protease inhibitors with the attachment of an appropriate amino aldehyde to the C‐terminus. Picomolar inhibitors of cathepsin L and S are reported and the mode of binding of one example to the model protease chymotrypsin is defined by X‐ray crystallography. 相似文献
66.
Two‐Component Supramolecular Gels Derived from Amphiphilic Shape‐Persistent Cyclo[6]aramides for Specific Recognition of Native Arginine 下载免费PDF全文
Youzhou He Min Xu Rongzhao Gao Xiaowei Li Fengxue Li Xuedan Wu Prof. Dingguo Xu Dr. Huaqiang Zeng Prof. Lihua Yuan 《Angewandte Chemie (International ed. in English)》2014,53(44):11834-11839
A unique supramolecular two‐component gelation system was constructed from amphiphilic shape‐persistent cyclo[6]aramides and diethylammonium chloride (or triethylammonium chloride). This system has the ability to discriminate native arginine from 19 other amino acids in a specific fashion. Cyclo[6]aramides show preferential binding for the guanidinium residue over ammonium groups. This specificity was confirmed by both experimental results and theoretical simulations. These results demonstrated a new modular displacement strategy, exploring the use of species‐binding hydrogen‐bonded macrocyclic foldamers for the construction of two‐component gelation systems for selective recognition of native amino acids by competitive host–guest interactions. This strategy may be amenable to developing a variety of functional two‐component gelators for specific recognition of various targeted organic molecular species. 相似文献
67.
Pingchun Wei Kai Zhang Dr. Xin Li Deying Meng Prof. Dr. Hans Ågren Prof. Dr. Zhongping Ou Prof. Dr. Seikweng Ng Prof. Dr. Hiroyuki Furuta Prof. Dr. Yongshu Xie 《Angewandte Chemie (International ed. in English)》2014,53(51):14069-14073
The first neo‐confused hexaphyrin(1.1.1.1.1.0) was synthesized by oxidative ring closure of a hexapyrrane bearing two terminal “confused” pyrroles. The new compound displays a folded conformation with a short interpyrrolic C???N distance of 3.102 Å, and thus it readily underwent ring fusion to afford a neo‐fused hexaphyrin with an unprecedented 5,5,5,7‐tetracyclic ring structure. Furthermore, coordination of CuII triggered a ring opening/contracting reaction to afford a CuII complex of an N‐linked pentaphyrin derivative. The roles of reactive N? C bonds in the porphyrinoid macrocycles were demonstrated. 相似文献
68.
Dr. Guangwu Li Prof. Taisuke Matsuno Yi Han Dr. Hoa Phan Shaofei Wu Dr. Qing Jiang Ya Zou Prof. Hiroyuki Isobe Prof. Jishan Wu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(24):9814-9822
Synthesis of fully conjugated cyclophanes containing large-size polycyclic aromatics is challenging. Now, three benzidine-linked, hexa-peri-hexabenzocoronene (superbenzene)-based ortho-, para-, and meta-cyclophanes are synthesized through intermolecular Yamamoto coupling reaction of structurally pre-organized precursors. Subsequent oxidative dehydrogenation gave the corresponding quinoidal benzidine-linked cyclophanes. Their geometries were confirmed by X-ray crystallographic analysis and their electronic properties were investigated by electronic absorption, cyclic voltammetry, and DFT calculations. The quinoidal benzidine-linked cyclophanes show thermally populated paramagnetic activity with a relatively large singlet-triplet energy gap. Two enantiomers for the ortho-cyclophanes ( 1-NH and 1-N ) were isolated and their chiral figure-of-eight macrocyclic structures were identified. The cage-like cyclophanes 2-NH and 3-NH with concave surface can selectively encapsulate fullerene C70. 相似文献
69.
Bartosz Szyszko Paweł Rymut Maksym Matviyishyn Agata Białońska Lechosław Latos-Grażyński 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):20312-20321
Di-2,7-naphthihexaphyrin(1.1.1.1.1.1), a non-aromatic carba-analogue of the hexaphyrin(1.1.1.1.1.1), incorporating two built-in 2,7-naphthylene moieties was synthesized as two separate, conformationally locked stereoisomers. Both conformers followed complex protonation pathways involving structurally different species, which can be targeted under kinetic and thermodynamic control. The neutralization of the ultimate dicationic product, accessible from both stereoisomers of the free base, allowed to realize the complex conformational switching cycle involving six structurally different species. 相似文献
70.
Mei-Ling Tan Dr. Qing-Hui Guo Dr. Xue-Yuan Wang Tan-Hao Shi Dr. Qian Zhang Sheng-Kai Hou Prof. Dr. Shuo Tong Prof. Dr. Jingsong You Prof. Dr. Mei-Xiang Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23857-23866
Despite the aesthetically appealing structures and tantalizing physical and chemical properties, zigzag hydrocarbon belts and their heteroatom-embedded analogues remain challenging synthetic targets. We report herein the synthesis of diverse O/N-doped zigzag hydrocarbon belts based on selective bridging of the fjords of resorcin[4]arene derivatives through intramolecular SNAr and palladium-catalyzed intermolecular C−N bond formation reactions. Preorganized conformations of mono-macrocyclic, half-belt and quasi-belt compounds were revealed to facilitate cyclization reactions to construct heteroatom-linked octahydrobelt[8]arenes. The acquired products had strained square-prism-shaped belt structures in which all six-membered heterocyclic rings adopted an unusual boat conformation with equatorially configured alkyl groups. The unprecedented heteroatom-bearing belts also exhibited different photophysical and redox properties to those of octahydrobelt[8]arene analogues. 相似文献