季戊四醇的超分子化学

介绍季戊四醇的超分子化学,包括超分子网状结构、螺环冠醚、非常规液晶、富勒烯衍生物、固相光催化反应、Janus树枝状分子等等。     

Planar Chiral Phosphines Derived from [2.2]Paracyclophane

[2.2]Paracyclophane offers an exciting framework for the synthesis of planar chiral phosphines. Its rigid structure and unusual electronic properties have led to the development of a range of mono- and di-phosphines including the commercially available ligand, PhanePhos. This review discusses the synthesis and use of [2.2]paracyclophane-based phosphines and aims to give an insight into their success and failures. It is hoped that this review will encourage the design of new planar chiral phosphines for use in transition metal-mediated catalysis and organocatalysis.     

Cyclophnes的合成进展

Cyclophanes是一类芳环通过烷基桥连接而成的大环化合物，是超分子化学中的受体，本文按全碳、含杂原子、笼形分类Cyclophanes,对其各类的合成进行综述。     

A new planar chiral bipyridine-ligand: pyrid-2-yl[2](1,4)benzeno[2](5,8)quinolino-phane

The synthesis of the new planar chiral heterocyclic nitrogen ligand pyrid-2-yl[2](1,4)benzeno[2](5,8)quinolino-phane ( 1 with [2.2]paracyclophane-skeleton is described. The enantiomeric resolution is achieved by HPLC. The CD-spectra of 1 and of its chiral quinoline precursor are recorded. The enantiomerically pure title compound 1 is used in copper-catalyzed asymmetric cyclopropanation of styrene and in asymmetric iridium-catalyzed transfer-hydrogenation of acetophenone.     

Direct Synthesis of Polyaromatic Cyclophanes Containing Bis-Methylene-Interrupted Z-Double Bonds and Study of Their Antitumor Activity In Vitro

An original synthetic route was developed for the preparation of previously unknown unsaturated polyaromatic macrolactones containing a 1Z,5Z-diene moiety in 48–71% yields and with >98% stereoselectivity. The method is based on intermolecular cyclocondensation of aromatic dicarboxylic acids with α,ω-alka-nZ,(n+4)Z-dienediols (1,12-dodeca-4Z,8Z-dienediol, 1,14-tetradeca-5Z,9Z-dienediol, 1,18-octadeca-7Z,11Z-dienediol) mediated by N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDC)/4-dimethylaminopyridine (DMAP). The unsaturated diols were prepared by successive homo-cyclomagnesiation of tetrahydropyran ethers of O-containing 1,2-dienes with EtMgBr in the presence of Mg metal and the Cp₂TiCl₂ catalyst (10 mol.%) and subsequent treatment with 0.1 equiv. of para-toluenesulfonic acid of pyran ethers formed after the acid hydrolysis of magnesacyclopentanes. The resulting cyclophanes exhibited high cytotoxic activity in vitro against Jurkat, K562, U937, and HL60 cancer lines. Additionally, the synthesized products were studied for their effect on mitochondria, ability to induce apoptosis, and influence on the cell cycle using modern flow cytometry methods.     

Paracyclophanes in Action: Asymmetric Catalytic Dialkylzinc Addition to Imines Using [2.2]Paracyclophane-based N,O-Ligands as Catalysts

The asymmetric addition of dibutylzinc to imines is achieved by employing [2.2]paracyclophane-based ketimine ligands with good to excellent enantioselectivities. A comparison to other organozinc reagent is made.     

Highly Stereoselective Synthesis of Novel Multistereogenic Bis‐Bifunctional Ligands Based on [2.2]Paracyclophane‐ 4,7‐quinone,their Structure Elucidation and Application in Asymmetric Catalysis

Bis‐bifunctional cis‐4,7‐diarylsubstituted‐4,7‐dihydroxy‐4,7‐dihydro[2.2]paracyclophanes 3–6 were synthesized by a highly diastereoselective reaction of ortho‐substituted aryllithium reagents with [2.2]paracyclophane‐4,7‐quinone ( 1 ). Enantiomerically pure diols 3–5 were tested as chiral inductors in the enantioselective addition of diethylzinc to benzaldehyde (up to 93.5% ee). Acid dehydration of cis‐4,7‐di(2‐methoxyphenyl)‐4,7‐dihydroxy‐4,7‐dihydro[2.2]paracyclophane ( 3 ) results in 4,7‐dihydro‐7,8‐di(2‐methoxyphenyl)[2.2]paracyclophane‐4‐one ( 8 ) – a planar chiral cyclohexadienone of the [2.2]paracyclophane series with a para‐semiquinoid substructure. X‐Ray investigations of compounds 3, 4 and 8 were performed.     

Pillarquinones and Pillararenequinones

Pillar[n]quinones and pillar[n-m]arene[m]quinones are oxidation products of pillar[n]arenes. Their molecular structure resembles the parent compounds. However, their map of electron density is different. Each 1,4-benzoquinone ring, which replaces a 1,4-dialkoxy-substituted benzene ring decreases the electron density in the interior cavity and increases the electron density on the upper and lower rim of the pillar. The electron donor character is stepwise transformed to an electron acceptor status. This effect alters the complexation tendencies, which are the most interesting properties of these macrocyclic host systems.     

Olefination Reactions in the Synthesis of Cyclophanes

A survey of olefination reactions that have been used in the synthesis of cyclophanes is presented. This covers the Ramberg–Bäcklund reaction, the Wittig and related reactions, the McMurry and related reactions, ring-closing metathesis (alkenes, alkynes and ene-ynes), aldol condensations and Siegrist reactions, as well as miscellaneous reactions. The McMurry reaction and ring-closing metathesis have enjoyed the greatest popularity in recent years, but they are typically used for complementary purposes. In virtually all cases, the McMurry reaction is used to install a two-carbon (1,2-ethenylene) bridge, whereas ring-closing metathesis is used to construct bridges that are at least four-membered, but usually considerably longer. Some well-known olefinations have seen little or no use in the field of cyclophane chemistry.