An intramolecular N‐arylation approach to 3‐functionalized 4,9‐dihydropyrrolo[2,1‐b]quinazolines

A series of 4,9‐dihydropyrrolo[2,1‐b]quinazolines containing electron withdrawing groups at the 3‐position have been prepared by the palladium‐catalyzed intramolecular N‐arylation of some 2‐aminopyrroles having a 2‐bromobenzyl group at the N‐1 position. Important for success of the reaction is the use of X‐phos, a biphenyl mono‐phosphine ligand, instead of xantphos, a more standard diphosphine ligand, and the use of t‐BuOH as reaction solvent. J. Heterocyclic Chem., (2011).     

Construction of π‐Surface‐Metalated Pillar[5]arenes which Bind Anions via Anion–π Interactions

By simple ligand exchange of the cationic transition‐metal complexes [(Cp*)M(acetone)₃](OTf)₂ (Cp*=pentamethylcyclopentadienyl and M=Ir or Rh) with pillar[5]arene, mono‐ and polynuclear pillar[5]arenes, a new class of metalated host molecules, is prepared. Single‐crystal X‐ray analysis shows that the charged transition‐metal cations are directly bound to the outer π‐surface of aromatic rings of pillar[5]arene. One of the triflate anions is deeply embedded within the cavity of the trinuclear pillar[5]arenes, which is different to the host–guest behavior of most pillar[5]arenes. DFT calculation of the electrostatic potential revealed that the metalated pillar[5]arenes featured an electron‐deficient cavity due to the presence of the electron‐withdrawing transition metals, thus allowing encapsulation of electron‐rich guests mainly driven by anion–π interactions.     

Thieno[2′,3′:5,6]azepino[2,1‐a]isoindolones from hydroxylactam‐alcohols via N‐acyliminium ion olefin cyclization

A one pot synthesis of thienoazepinoisoindolones from the reaction of hydroxylactam‐alcohols, under acidic treatment, is described via an N‐acyliminium olefin cyclization.     

A benzene‐rich pseudopolymorph of bis[μ‐1,3‐bis(pentafluorophenyl)propane‐1,3‐dionato]‐κ3O,O′:O′;κ3O:O,O′‐bis{aqua[1,3‐bis(pentafluorophenyl)propane‐1,3‐dionato‐κ2O,O′]nickel(II)} benzene tetrasolvate

The title complex comprises two Ni²⁺ ions, four fluorinated ligands and two water molecules in a centrosymmetric dinuclear complex. This compound was crystallized from benzene–CH₂Cl₂, and two types of crystals, viz. the title benzene tetrasolvate, [Ni₂(C₁₅HF₁₀O₂)₄(H₂O)₂]·4C₆H₆, (I), and the previously reported benzene disolvate, [Ni₂(C₁₅HF₁₀O₂)₄(H₂O)₂]·2C₆H₆, (II) [Hori et al. (2009). Bull. Chem. Soc. Jpn, 82 , 96–98], were obtained as pseudopolymorphs. In the crystal structure of (I), the four benzene solvent molecules interact closely with all the pentafluorophenyl groups of the complex through arene–perfluoroarene interactions. The molecular structures of the two compounds show essentially the same conformation, although the benzene molecules are accommodated in a columnar packing in (I), while they are isolated from each other in (II).     

Donor–acceptor‐integrated conjugated polymers based on carbazole[3,4‐c:5,6‐c]bis[1,2,5]thiadiazole with tight π–π stacking for photovoltaics

An original strategy to construct a new donor–acceptor (D–A)‐integrated structure by directly imposing “pull” unit on the “push” moiety to form fused ring architecture has been developed, and poly{N‐alkyl‐carbazole[3,4‐c:5,6‐c]bis[1,2,5]thiadiazole‐alt‐thiophene} (PCBTT) with D–A‐integrated structure, in which two 1,2,5‐thiadiazole rings are fixed on carbazole in 3‐, 4‐ and 5‐, 6‐position symmetrically and thiophene is used as bridge, has been synthesized. The interaction between pull and push units has fine tuned the HOMO/LUMO energy levels, and the resulting copolymer covers the solar flux from 300 to 750 nm. The interaction between pull and push units is worth noting that due to the fused five rings inducing strong intermolecular interaction, an extremely short π–π stacking distance of 0.32 nm has been achieved for PCBTT both in powder and solid states. This is the shortest π–π stacking distance reported for conjugated polymers. Additionally, an obvious intramolecular charge transfer and energy transfer from donor units to acceptor units have been detected in this D–A integration. A moderate‐to‐high open‐circuit voltage of ～0.7 V in PCBTT:[6,6]‐phenyl‐C61 butyric acid methyl ester (PCBM) (w/w = 1/2) solar cells is achieved due to the low‐lying HOMO energy level of PCBTT. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Silanol Mediated π‐Assembly of Extended N‐Heterocycles

Self‐assembly of silanetriols with 4,4′‐bipyridine affords infinite columns of cofacially arranged π‐stacks as evidenced by X‐ray data. Variation of the silanetriol reveals a subtle balance between hydrogen bonding and π interactions, which, by proper choice of the substituent, may foster either dominant hydrogen bonding or dominant π interaction.     

Diastereoselective access to chiral non‐racemic [1,3]oxazolo‐[2,3‐a]isoindol‐5‐one ring systems viaO‐cationic cyclization

Dedicated to Professor Jean Morel for his retirement The title compounds 4 have been prepared from suitable β‐amino‐ alcohol 2 and phthalic anhydride ( 5 ) in a three‐step sequence in moderate to good yields (58‐94%). The key step of this methodology is based on an intramolecular O‐cationic cyclization involving N‐acyliminium species. The high levels of the observed chemoselectivity during the intermolecular or intramolecular cyclization were also discussed.     

1,2,4‐Triazol‐3‐ylidenes with an N‐2,4‐Dinitrophenyl Substituent as Strongly π‐Accepting N‐Heterocyclic Carbenes

The synthesis and characterisation of a series of new Rh and Au complexes bearing 1,2,4‐triazol‐3‐ylidenes with a N‐2,4‐dinitrophenyl (N‐DNP) substituent are described. IR, NMR, single‐crystal X‐ray diffraction and computational analyses of the Rh complexes revealed that the N‐heterocyclic carbenes (NHCs) behaved as strong π acceptors and weak σ donors. In particular, a natural bond orbital (NBO) analysis revealed that the contributions of the Rh→C_carbene π backbonding interaction energies (ΔE_bb) to the bond dissociation energies (BDE) of the Rh? C_carbene bond for [RhCl(NHC)(cod)] (cod=1,5‐cyclooctadiene) reached up to 63 %. The Au complex exhibited superior catalytic activity in the intermolecular hydroalkoxylation of cyclohexene with 2‐methoxyethanol. The NBO analysis suggested that the high catalytic activity of the Au^I complex resulted from the enhanced π acidity of the Au atom.     

C—H⋯π and π–π interactions in the supramolecular structure of 3‐methyl‐1,4‐diphenyl‐1H‐pyrazolo[3,4‐b]pyridine

The supramolecular structure of the title compound, C₁₉H₁₅N₃, is defined by π–π‐stacking and C—H?π interactions. There are no conventional hydrogen bonds in the structure.     

1,3‐Diaxial Repulsion vs. π‐Delocalization in the 7‐Amino‐2,4‐diazabicyclo[3.3.1]nonan‐3‐one Skeleton

(1R,5S,6S,8R)‐6,8,9‐Trihydroxy‐3‐oxo‐2,4‐diazabicyclo[3.3.1]nonan‐7‐ammonium chloride hydrate ( 3 Cl⋅H₂O) and (1R,5S,6S,8R)‐7‐amino‐6,8,9‐trihydroxy‐2,4‐diazabicyclo[3.3.1]nonan‐3‐one ( 4 ) have been prepared, and their crystal structures have been determined from single‐crystal X‐ray diffraction data. Both compounds consist of a bicyclic skeleton with the three N‐atoms in an all‐cis‐1,3,5‐triaxial arrangement. Considerable repulsion between these axial N‐atoms is indicated by a significant distortion of the two cyclohexane chairs and by increased N⋅⋅⋅N distances. The lone pair of the free amino group of 4 is involved in intermolecular H‐bonding and is turned away from the adjacent carbonyl C‐atom of the urea moiety. The structural properties together with the observed reactivity do not provide any evidence for an intramolecular donor‐acceptor interaction between the carbonyl C‐ and the amine N‐atom.     

A [4π+4π] intramolecular photocyclomer of 9‐anthroic anhydride: 5,6,11,12‐tetrahydro‐5,12;6,11‐di‐o‐­benzenodibenzo[a,e]cyclooctene‐5,6‐dicarboxylic anhydride

The title compound, C₃₀H₁₈O₃, was obtained by light irradiation of a di­chloro­ethane solution of 9‐anthroyl chloride and 9‐anthroic acid. The mol­ecules, which possess approximately mm2 local symmetry, are packed in columns, the oxy­genated moieties facing each other according to the symmetry of a monoclinic lattice. The space group of the crystal is P2₁/c, with a whole mol­ecule as the asymmetric unit. The structure is compared with those of similar dianthracene derivatives.     

Weak C—H...O and C—H...π hydrogen bonds and π–π stacking interactions in a series of four N′‐[(E)‐(aryl)methylidene]‐N‐methyl‐2‐oxo‐1,3‐oxazolidine‐4‐carbohydrazides

Oxazolidin‐2‐ones are widely used as protective groups for 1,2‐amino alcohols and chiral derivatives are employed as chiral auxiliaries. The crystal structures of four differently substituted oxazolidinecarbohydrazides, namely N′‐[(E)‐benzylidene]‐N‐methyl‐2‐oxo‐1,3‐oxazolidine‐4‐carbohydrazide, C₁₂H₁₂N₃O₃, (I), N′‐[(E)‐2‐chlorobenzylidene]‐N‐methyl‐2‐oxo‐1,3‐oxazolidine‐4‐carbohydrazide, C₁₂H₁₂ClN₃O₃, (II), (4S)‐N′‐[(E)‐4‐chlorobenzylidene]‐N‐methyl‐2‐oxo‐1,3‐oxazolidine‐4‐carbohydrazide, C₁₂H₁₂ClN₃O₃, (III), and (4S)‐N′‐[(E)‐2,6‐dichlorobenzylidene]‐N,3‐dimethyl‐2‐oxo‐1,3‐oxazolidine‐4‐carbohydrazide, C₁₃H₁₃Cl₂N₃O₃, (IV), show that an unexpected mild‐condition racemization from the chiral starting materials has occurred in (I) and (II). In the extended structures, the centrosymmetric phases, which each crystallize with two molecules (A and B) in the asymmetric unit, form A+B dimers linked by pairs of N—H...O hydrogen bonds, albeit with different O‐atom acceptors. One dimer is composed of one molecule with an S configuration for its stereogenic centre and the other with an R configuration, and possesses approximate local inversion symmetry. The other dimer consists of either R,R or S,S pairs and possesses approximate local twofold symmetry. In the chiral structure, N—H...O hydrogen bonds link the molecules into C(5) chains, with adjacent molecules related by a 2₁ screw axis. A wide variety of weak interactions, including C—H...O, C—H...Cl, C—H...π and π–π stacking interactions, occur in these structures, but there is little conformity between them.