Synthesis of oxacalixarenes incorporating nitrogen heterocycles: evidence for thermodynamic control.

[structure: see text] Oxacalix[2]arene[2]hetarenes are formed in a single step by cyclooligomerization of meta-diphenols with meta-dichlorinated azaheterocycles. The high selectivity for cyclic tetramer formation results from thermodynamic product control. Macrocycles as large as oxacalix[5]arene[5]hetarenes have been isolated under nonequilibrating conditions.

Tandem Incorporation of Enantiomeric Residues Engenders Discrete Peptoid Structures.

A new peptoid design strategy entailing the concurrent inclusion of enantiomeric side chains enabled the construction of several new structural motifs, including a newly characterized "ω-strand". This new architectural technique significantly expands peptoid structural and functional space and can potentially be applied to other foldameric systems.

Single-step synthesis of D3h-symmetric bicyclooxacalixarenes.

Bicyclooxacalixarenes are obtained in up to 95% yield by condensation of phloroglucinol with electron-poor meta-dihalogenated benzenes or pyridines. Single-crystal X-ray analysis reveals that these compounds adopt highly symmetrical, all-1,3-alternate cage-like structures. [structure: see text]

Synthesis of functionalized oxacalix[4]arenes.

Tetranitrooxacalix[4]arenes are generated in high yield by the room-temperature S(N)Ar reaction of 1,3-dihydroxybenzenes with 1,5-difluoro-2,4-dinitrobenzene. The reaction is tolerant to a range of functionality on the nucleophilic component, including hydroxyl-substitution at the 2- and 5-positions, which yields previously unknown 26,28- and 5,17-dihydroxyoxacalix[4]arenes.

Synthesis and Characterization of Copper(I) Complexes with a Fairly Bulky Tris(pyrazolyl)hydroborate Ligand. Probing the Flexibility of the Metal-Containing Pocket Formed by the Ligand.

Four copper(I) tris(pyrazolyl)hydroborate complexes are reported with the fairly bulky tris[3-(p-tert-butylphenyl)-5-methylpyrazol-1-yl]hydroborate ligand (Tp()t(Bu-)(Ph,Me)). Tp()t(Bu-)(Ph,Me)Cu(CH(3)CN) (1) was synthesized from CuCl and Tp()t(Bu-)(Ph,Me)Li(CH(3)CN). The acetonitrile ligand in 1 was easily replaced by CO, PPh(3), and P(t)()Bu(3), forming Tp()t(Bu-)(Ph,Me)Cu(CO) (2), Tp()t(Bu-)(Ph,Me)Cu(PPh(3)) (3), and Tp()t(Bu-)(Ph,Me)Cu(P(t)()Bu(3)) (4), respectively. Complexes 1-4 have been crystallographically characterized. 1.4CH(3)CN, 173 K: C(52)H(67)BCuN(11), triclinic, P&onemacr;, a = 13.4201(10) Å, b= 15.132(2) Å, c = 15.2125(13) Å, alpha = 60.743(6) degrees, beta = 73.211(4) degrees, gamma = 74.839(5) degrees, Z = 2, R1 = 6.81% (wR2 = 18.91%). 2, 296 K: C(43)H(52)BCuN(6)O, monoclinic, C2/c, a = 25.592(4) Å, b = 12.434(2) Å, c = 28.044(3) Å, beta = 104.073(9) degrees, Z = 8, R1 = 7.47% (wR2 = 22.08%). 3.CH(2)Cl(2), 173 K: C(61)H(69)BCl(2)CuN(6)P, triclinic, P&onemacr;, a= 12.5080(13) Å, b = 15.159(3) Å, c = 17.151(2) Å, alpha = 64.271(10) degrees, beta = 79.073(7) degrees, gamma = 86.572(8) degrees, Z = 2, R1 = 5.13% (wR2 = 13.28%). 4.0.5 hexane, 298 K: C(57)H(86)BCuN(6)P, triclinic, P&onemacr;, a = 13.337(2) Å, b = 13.435(2) Å, c = 17.386(2) Å, alpha = 88.371(7) degrees, beta = 71.863(8) degrees, gamma = 80.223(9) degrees, Z = 2, R1 = 6.96% (wR2 = 18.62%). The Tp()t(Bu-)(Ph,Me) ligands in 1, 2, and 3 bind in a tridentate fashion; the CH(3)CN and CO ligands fit comfortably within the pocket formed by the tert-butylphenyl substituents and the PPh(3) ligand interleaves between the pyrazole arms. The flexibility of the pocket was probed by calculating the area of the triangle created by connecting the midpoints of the 3-phenyl groups; this parameter increases by 15% for 3 (the largest) over 1 (the smallest). Thus, the pocket exhibits some flexibility, found to be due to both steric and electronic factors. Complex 4 features a bidentate Tp()t(Bu-)(Ph,Me) ligand as the P(t)()Bu(3) apparently exceeds the pocket's flexibility.

Copper(I) Complexes with a NS(2)-Macrocyclic Ligand Bearing a Pendant Naphthyl Group: Structures of {N-[2-(1-Naphthyl)ethyl]-1-aza-4,8-dithiacyclodecane}copper(I)-Ligand, where Ligand = eta(2)-Naphthalene, Acetonitrile, or Triphenylphosphine.

A new macrocyclic ligand with a pendant naphthalene group, N-[2-(1-naphthyl)ethyl]-1-aza-4,8-dithiacyclodecane (L), has been synthesized and characterized. The copper(I)-acetonitrile complex [LCu(CH(3)CN)](PF(6)) (1) was synthesized from L and [Cu(CH(3)CN)(4)](PF(6)). The acetonitrile ligand from 1 was easily removed to give [LCu](PF(6)) (2). Complexes 1 and 2 have been crystallographically characterized. 1: C(21)H(28)N(2)CuF(6)PS(2), triclinic, P&onemacr;, a = 11.1901(10) Å, b = 11.2735(12) Å, c = 12.1350(10) Å, alpha = 98.996(8) degrees, beta = 117.188(6) degrees, gamma = 105.354(7) degrees, Z = 2, R1 = 0.0505 (wR2 = 0.1418). 2.0.5hexane: C(22)H(31)NCuF(6)PS(2), monoclinic, P2(1)/c, a = 15.7318(15) Å, b = 8.9164(10) Å, c = 17.205(5) Å, beta = 102.431(6) degrees, Z = 4, R1 = 0.0587 (wR2 = 0.1545). In addition, a cocrystallized mixture of both complexes was crystallographically characterized. 1&2.hexane: C(46)H(61)N(3)Cu(2)F(12)P(2)S(4), triclinic, P&onemacr;, a = 10.8308(9) Å, b = 12.6320(8) Å, c = 19.9412(13) Å, alpha = 80.445(5) degrees, beta = 76.405(6) degrees, gamma = 78.825(5) degrees, Z = 2, R1 = 0.0661 (wR2 = 0.1871). The solid-state structure of 2 features the pendant naphthalene group bound in an eta(2)-fashion, which is highly unusual for copper complexes. In CDCl(3), 2 exhibits fluxional behavior with the barrier to the process estimated, DeltaG() = 12-13 kcal. Variable temperature NMR spectroscopy gave compelling evidence for solution binding of the naphthalene group in 2, apparently the first example for copper(I). The fluxional process seen for 1 is best described as interconversion of the two enantiomers via a species with an unbound naphthalene group. Consistent with the weak binding of the naphthalene group, it is readily replaced with other ligands, such as triphenylphosphine to form [LCu(PPh(3))](PF(6)) (3). Complex 3 has also been structurally characterized: C(37)H(40)NCuF(6)P(2)S(2), monoclinic, P2(1)/c, a = 11.462(2) Å, b = 15.972(2) Å, c = 19.835(9) Å, beta = 94.50(3) degrees, Z = 4, R1 = 0.0906 (wR2 = 0.1889).

Polymorphic di-2-pyridyl ketone 4-nitrophenylhydrazone (dpknph): the structure of beta-dpknph.

A new polymorph of di-2-pyridyl ketone 4-nitrophenylhydrazone [alternative name: N-(dipyridin-2-ylmethylene)-N'-(4-nitrophenyl)hydrazine], C17H13N5O2, isolated from the filtrate of a sonicated acetonitrile solution of dpknph and CdCl2, was found to crystallize in the monoclinic space group P21/c, in contrast to the known form which crystallizes in P21/n. The non-coplanar molecules pack in parallel stacks without any intermolecular hydrogen-bonding interactions. This packing pattern contrasts with the interlocked interdigitated packing seen in the previously known polymorph.