Stable pi-dimer of a tetrathiafulvalene cation radical encapsulated in the cavity of cucurbit[8]uril

The first stable pi-dimer of a tetrathiafulvalene (TTF) cation radical encapsulated in the cavity of cucurbit[8]uril has been isolated at room temperature and fully characterized; it shows absorption bands at 400, 540 and 760 nm, characteristic of the TTF cation radical dimer.     

The first carborane triflates: synthesis and reactivity of 1-trifluoromethanesulfonylmethyl- and 1,2-bis(trifluoromethanesulfonylmethyl)-o-carborane

The first carborane triflates, namely, 1-trifluoromethanesulfonylmethyl-o-carborane (2) and 1,2-bis(trifluoromethanesulfonylmethyl)-o-carborane (7), were obtained in high yields in the reactions of 1-hydroxymethyl-o-carborane (1) or 1,2-bis(hydroxymethyl)-o-carborane (6) with triflic anhydride (Tf2O) in CH2Cl2 in the presence of pyridine. When an excess of pyridine is employed, 1-o-carboranylmethylpyridinium triflate (3), which retains a closo-icosahedral structure, or a pyridinium salt (4) with a zwitterionic nido-dicarbaundecaborate anion are obtained from 1, while the nido compound 8 is formed from 6. The reaction of compound 2 or 7 with excess pyridine also gave 3 or 8, respectively. Compound 2 proved to be a convenient carboranylmethylating agent which reacts with nucleophiles (e.g., potassium phthalimide, PPh3 or KCN) to give the corresponding substitution products N-[(o-carboranyl-1-yl)methyl]phthalimide (9), o-carboranylmethylphosphonium salt 10, and 1-cyanomethyl-o-carborane (11). All compounds were characterized by 1H and 11B NMR spectroscopy. The structures of compounds 4, 7 and 8 were established by X-ray analysis.     

Nickel(II) macrocyclic complexes with long alkyl pendant chain: synthesis,x-ray structure,and anion exchange property in the solid state

A nickel(II) pentaaza macrocyclic complex containing a 1-hexadecyl pendant chain, [Ni(C(25)H(55)N(5))](ClO(4))(2).H(2)O (1), was synthesized by a one-pot metal-template condensation reaction. Crystal data for 1: triclinic, Ponemacr;, a = 8.333(4) A, b = 8.356(3) A, c = 28.374(9) A, alpha = 81.865(19) degrees, beta = 86.242(18) degrees, gamma = 63.871(17) degrees, Z = 2. Solid 1 forms hydrophobic layers that are constructed by the long alkyl chains of the macrocycles. Solid 1 exchanges ClO(4)(-) with NCS(-), PF(6)(-), C(2)O(4)(2-), NO(3)(-), and CF(3)SO(3)(-) that are dissolved in water. From the reaction of [Ni(C(25)H(55)N(5))Cl(2)] with Et(3)NH(TCNQ)(2) in EtOH/DMF/acetone solution, [Ni(C(25)H(55)N(5))(TCNQ)(2)](TCNQ).(CH(3)COCH(3)) (2) (TCNQ = 7,7,8,8-tetracyano-p-quinodimethane) was prepared. Crystal data for 2: triclinic, Ponemacr;, a = 8.459(0) A, b = 13.945 (1) A, c = 26.833(2) A, alpha = 88.744(2) degrees, beta = 84.536(2) degrees, gamma = 80.089(4) degrees, Z = 2. In 2, TCNQ anions coordinate nickel(II) at the axial sites, which form pi-stacked TCNQ(-) dimers to give rise to 1-D chains. The neutral TCNQ molecules are included between the dimerized TCNQ(-) species, which construct a pi-stacked group of six TCNQ units as blocked by the long alkyl chains. Compound 2 is an electric insulator. It shows a weak signal in the EPR spectrum. The magnetic susceptibility data of 2 measured at 5-300 K exhibit a simple paramagnetism at low temperatures (<100 K) but an increase in the magnetic moment at higher temperatures due to the contribution of a thermally accessible triplet state for the antiferromagnetically coupled [TCNQ](2)(2-).     

Novel stereoselective synthesis of functionalized oxazolidinones from chiral aziridines

Enantiomerically pure N-(R)-alpha-methylbenzyl-4(R)-(chloromethyl)oxazolidinones (4R)-5a-k were synthesized in one step and high yields from various aziridine-2-methanols (S)-2a-k by intramolecular cyclization with phosgene. The alpha-methylbenzyl substituent on the nitrogen was easily cleaved to give both enanatiomers of 4-(chloromethyl)oxazolidinones (R)-7a and (S)-7a. (R)-7a was used for the efficient syntheses of (L)-homophenylalaninol analogues (S)-12a-j. We also applied the same methodology to prepare oxazolidinones 9a-c containing a heteroatom-substituted alkyl group at C-4 in high yields.