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PubMed1997

Macrocyclic Cu(II)(2), Cu(II)(4), Ni(II)(3), and Ni(II)(4) Complexes: Magnetic Properties of Tetranuclear Systems.

A binuclear tetraprotonated macrocyclic complex [Mg(2)(L(2)-H(4))(NO(3))(2)](NO(3))(2).6H(2)O (1) has been obtained by template condensation of 4-methyl-2,6-diformylphenol and 1,2-diaminoethane in the presence of magnesium acetate and nitrate. Complex 1 on reduction with NaBH(4), followed by the removal of magnesium, yields the 36-membered octaaminotetraphenol macrocyclic ligand H(4)L(1). The replacement of magnesium in 1 with copper(II) leads to the formation of the binuclear complex [Cu(2)L(3)(ClO(4))(2)] (2) derived from the [2+2] cyclization product of 4-methyl-2,6-diformylphenol and 1,2-diaminoethane. From H(4)L(1) a series of tetranuclear nickel(II) complexes 5-8 with the core cation [Ni(4)L(1)(&mgr;(2)-X)(2)(&mgr;(2)-H(2)O)(2)](2+) (X = NCS, N(3), OAc, or Cl) have been synthesized and characterized. The trinuclear complex [Ni(3)L(1)(acac)(2)(H(2)O)(2).2H(2)O (9), obtained by reacting nickel(II) acetylacetonate with H(4)L(1), on treatment with nickel(II) perchlorate produces the tetranuclear compound [Ni(4)L(1)(acac)(2)(H(2)O)(4)](ClO(4))(2) (10). Variable-temperature (4-300 K) magnetic susceptibility measurements have been carried out for the tetracopper(II) complex [Cu(4)L(1)(H(2)O)(4)](ClO(4))(4) (3) and the tetranickel(II) complexes [Ni(4)L(1)(&mgr;(3)-OH)(&mgr;(2)-H(2)O)(2)(ClO(4))](ClO(4))(2).2CH(3)COCH(3).H(2)O (4), [Ni(4)L(1)(&mgr;(2)-NCS)(2)(&mgr;(2)-H(2)O)(2)](ClO(4))(2).2CH(3)CN (5), [Ni(4)L(1)(&mgr;(2)-N(3))(2)(&mgr;(2)-H(2)O)(2)](ClO(4))(2).2CH(3)OH (6), [Ni(4)L(1)(&mgr;(2)-OAc)(2)(&mgr;(2)-H(2)O)(2)](ClO(4))(2).2H(2)O (7), and [Ni(4)L(1)(&mgr;(2)-Cl)(2)(&mgr;(2)-H(2)O)(2)]Cl(2).4H(2)O (8). The X-ray structure of 5 has been determined. The complex (C(50)H(70)N(12)O(14)Cl(2)S(2)Ni(4)) crystallizes in the triclinic space group P&onemacr; with a = 11.794(6) Å, b = 12.523(4) Å, c = 12.794(5) Å, alpha = 117.28(5) degrees, beta = 96.38(4) degrees, gamma = 109.65(3) degrees, and Z = 1. In the asymmetric unit each of the nickel(II) centers with distorted octahedral geometry is triply-bridged by a phenoxide group, a water molecule, and a N-bonded thiocyanate and these metal centers are further bridged to their symmetry-related counterparts by another phenoxide group. The experimental susceptibility data have been analyzed using appropriate Heisenberg spin coupling models (H = -2J(ij)()S(i)().S(j)()) and the best-fit spin exchange parameters obtained are as follows: J = -288(3) cm(-)(1) (3); J(1) = -8.1(2) cm(-)(1), J(2) = -10.2(2) cm(-)(1) (4); J(1) = -34.5(1.0) cm(-)(1), J(2) = -9.5(2.0) cm(-)(1) (5); J(1) = -34(1) cm(-)(1), J(2) = 11(2) cm(-)(1) (6); J(1) = -30(1) cm(-)(1), J(2) = -7.0(1.5) cm(-)(1) (7); J(1) = -32(1) cm(-)(1), J(2) = -4(1) cm(-)(1) (8).

Journal Article↗
PubMed1998

Reactivity of the Verdoheme Analogues, 5-Oxaporphyrin Complexes of Cobalt(II) and Zinc(II), with Nucleophiles: Opening of the Planar Macrocycle by Alkoxide Addition To Form Helical Complexes.

The 5-oxaporphyrin macrocycle is a modified porphyrin (with an oxygen atom replacing a meso-methine unit) that is produced during heme degradation in biological and chemical systems. We have undertaken an investigation into the chemical reactivity of metal complexes of this macrocycle. Here we report that the diamagnetic zinc(II) and paramagnetic cobalt(II) verdoheme analogues, [Zn(II)(OEOP)](O(2)CCH(3)) and [Co(II)(OEOP)](PF(6)) (OEOP is the monoanion of octaethyl-5-oxaporphyrin), undergo ring opening when treated with alkoxide ions. The zinc(II) complex Zn(II)(OEBOMe), where OEBOMe is the dianion of octaethylmethoxybiliverdin, is sufficiently stable to be isolated in crystalline form, but the cobalt(II) analogue, Co(II)(OEBOMe), is less stable and has been characterized primarily by (1)H NMR spectroscopy in solution. The reactions are accompanied by a color change from blue-green for the verdoheme complexes to yellow-green for the ring-opened compounds. The ring-opened product Zn(II)(OEBOMe) has been subjected to a crystallographic study which reveals that the complex contains a four-coordinate zinc(II) ion whose geometry is significantly controlled by the helical tetrapyrrole ligand so that tetrahedral coordination is not achieved. The structure of this complex is compared to that of a closely related free ligand and those of copper and cobalt complexes of tetrapyrrole ligands that also form helical complexes.

Journal Article↗
PubMed1998

A Novel Mixed Macrocycle Complex of Nickel: Synthesis, Structure, and Redox Chemistry of [Ni(II)([9]aneN(3))([9]aneS(3))](ClO(4))(2).CHCl(3) ([9]aneN(3) = 1,4,7-Triazacyclononane and [9]aneS(3) = 1,4,7-Trithiacyclononane).

The mixed macrocycle cation, [Ni([9]aneN(3))([9]aneS(3))](2+) (where [9]aneN(3) = 1,4,7-triazacyclononane and [9]aneS(3) = 1,4,7-trithiacyclononane), has been prepared by stepwise complexation of [9]aneN(3) and [9]aneS(3), respectively, to Ni(II) cation. The intermediate [Ni([9]aneN(3))(CH(3)NO(2))(3)](2+) has been isolated and characterized by mass spectrometry and UV-visible spectroscopy. Cyclic voltammetry of [Ni([9]aneN(3))(CH(3)NO(2))(3)](2+) shows a quasireversible wave for the Ni(II/III) couple (E(1/2) = 0.73V vs Fc(+/0)), and the Ni(III) species exhibits an axial ESR spectrum (g( perpendicular) = 2.101 and g( parallel) = 1.985). The structure of [Ni([9]aneN(3))([9]aneS(3))](ClO(4))(2).CHCl(3) has been determined. It crystallizes in monoclinic space group P2(1)/c with a = 13.3911(8) Å, b = 14.4430(9) Å, c = 13.6116(8) Å, beta = 107.2090(10) degrees, V = 2514.7(3) Å(3), and Z = 4. Of the 15 047 reflections collected, 5765 reflections (I > 2sigma(I)) were used in the refinement to obtain a final R(w) = 0.0278 and R(F) = 0.0368. In the cation [Ni([9]aneN(3))([9]aneS(3))](2+), the two macrocycles occupy the trigonal faces of the Ni(2+) ion, imposing a distorted octahedral geometry. Cyclic voltammetry of the complex in CH(3)CN (Pt electrodes, 0.1 M n-Bu(4)NClO(4), 500 mV) shows a quasireversible wave for the Ni(II)/Ni(III) couple (E(1/2) = 0.86V vs Fc(+/0)). Chemical oxidation by NOPF(6) of the cation [Ni([9]aneN(3))([9]aneS(3))](2+) generates a Ni(III) species that shows axial ESR spectrum with g( perpendicular) = 2.106 and g( parallel) = 2.063. No characteristic reduction wave was observed in either CH(3)CN or CH(3)NO(2) media.

Journal Article↗
PubMed1998

Structural and (99)Tc NMR Investigations of Complexes with fac-[Tc(CO)(3)](+) Moieties and Macrocyclic Thioethers of Various Ring Sizes: Synthesis and X-ray Structure of the Complexes fac-[Tc(9-ane-S(3))(CO)(3)]Br, fac-[Tc(2)(tosylate)(2)(18-ane-S(6))(CO)(6)], and fac-[Tc(2)(20-ane-S(6)-OH)(CO)(6)][tosylate](2).

Starting originally from the organometallic precursor [NEt(4)](2)[TcBr(3)(CO)(3)] (1b), substitution reactions were performed with the macrocyclic thioethers 1,4,7-trithiacyclononane (9-ane-S(3)), 1,4,7,10,13,16-hexathiacyclooctadecane (18-ane-S(6)), and 3,6,9,13,16,19-hexathiacycloicosanol (20-ane-S(6)-OH). The corresponding complexes fac-[Tc(9-ane-S(3))(CO)(3)]Br (2), fac-[Tc(2)(tosylate)(2)(18-ane-S(6))(CO)(6)] (3), and fac-[Tc(2)(20-ane-S(6)-OH)(CO)(6)][tosylate](2) (5) were isolated in good yields and characterized spectroscopically by IR, (1)H, (99)Tc NMR, and X-ray diffraction methods. In the case of 18-ane-S(6) and 20-ane-S(6)-OH the formation of the 1:2 as well as the 1:1 complex could be observed in the (99)Tc NMR experiment, depending on the ligand to metal ratio. Complex 2crystallizes in the monoclinic space group P2(1)/c, a = 14.79(2) Å, b = 11.691(2) Å, c = 16.94(2) Å, beta = 94.88(6) degrees, Z = 8. The tripodal ligand is coordinated through the sulfur atoms to the metal center, forming three favorable five-membered chelate rings. Complex 3 crystallizes in the monoclinic space group C2/c, a = 26.073(4) Å, b = 9.288(1) Å, c = 17.898(3) Å, beta = 99.84(1) degrees, Z = 4. The binuclear unit is formed by two fac-[Tc(tosylate)(CO)(3)] moieties which are trans, bidentate coordinated to the macrocyclic ligand. Compound 5 crystallizes in the monoclinic space group Pc, a = 25.737(4) Å, b = 14.009(1) Å, c = 26.479(3) Å, beta = 149.56(2) degrees, Z = 4. In the case of the dicationic compound 5, the two Tc(I) centers are tripodal, cis coordinated toward the thia crown ether. A detailed analysis of the ring conformation in the solid state structure explained to a certain extent the formation of only one isomer (trans in the case of 3 and cis in the case of 5, respectively) during the substitution reaction.

Journal Article↗
PubMed1998

Aminotriazines as Locking Fragments in Macrocyclic Synthesis.

The macrocyclic compounds (6-(4',6'-diamino-1',3',5'-triazinyl)-1,4,6,8,11-pentaazacyclotetradecane)copper(II) triperchlorate dihydrate, [Cu(HL(2))](ClO(4))(3).2H(2)O, (6-(6'-amino-4'-oxo-1'H-1',3',5'-triazinyl)-1,4,6,8,11-pentaazacyclotetradecane)copper(II) diperchlorate hydrate, [CuL(3)](ClO(4))(2).H(2)O, and [(6-(4',6'-dioxo-1'H-1',3',5'-triazinyl)-1,4,6,8,11-pentaazacyclotetradecane)copper(II)] diperchlorate, [CuL(4)](ClO(4))(2), have been synthesized. The macrocycles synthesized contain respectively pendant melamine, ammeline, and ammelide rings. The X-ray cyrstallographic analyses of [Cu(HL(2))](ClO(4))(3).2H(2)O, triclinic, space group P&onemacr;, a = 9.489(10) Å, b = 12.340(2) Å, c = 24.496(4) Å, alpha = 87.74(10) degrees, beta = 85.51(10) degrees, gamma = 70.95(10) degrees, and Z = 4, and {[CuL(3)](ClO(4))(2).H(2)O}(2), monoclinic, space group C2/c, a = 18.624(8) Å, b = 17.160(2) Å, c = 15.998(6) Å, beta = 117.82(2) degrees, and Z = 4, are reported. The structure of [Cu(HL(2))](ClO(4))(3).2H(2)O shows the formation of linear tapes, formed by a combination of hydrogen bonds and pi-pi stacking interactions. The structure of [CuL(3)](ClO(4))(2).H(2)O displays formation of dimers, formed by a coordinate bond from the oxygen in one molecule to the copper atom of another. The tautomeric forms of the ammeline and ammelide moieties have been determined. The potential of these compounds as subunits for cocrystallization has been investigated.

Journal Article↗
PubMed1998

Pyramidal Inversion at Phosphorus Facilitated by the Presence of Proximate Lewis Acids. Coordination Chemistry of Group 13 Elements with the Macrocyclic Bis(amidophosphine) Ligand [P(2)N(2)] ([P(2)N(2)] = [PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh]).

Investigations on the preparation of four- and five-coordinate aluminum and gallium bis(amidophosphine) derivatives are reported. The reaction of the macrocyclic ligand precursor anti-Li(2)(THF)(2)[P(2)N(2)] ([P(2)N(2)] = [PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh]) with AlCl(3) or GaCl(3) in toluene at 25 degrees C leads to the formation of the four-coordinate species anti-MCl[P(2)N(2)] (M = Al (1), Ga (2)). An X-ray diffraction study of anti-GaCl[P(2)N(2)] shows it to be monomeric with a distorted tetrahedral geometry at Ga; only one of the phosphine donors of the [P(2)N(2)] ligand binds to the gallium, resulting in the retention of the anti-configuration. The solution NMR spectra are consistent with C(s)() symmetry. The addition of AlCl(3) or GaCl(3) to the macrocyclic ligand precursor syn-Li(2)(dioxane)[P(2)N(2)] in toluene at 25 degrees C yields the five-coordinate complexes syn-MCl[P(2)N(2)] (M = Al (3), Ga (4)). The X-ray crystal structure of syn-GaCl[P(2)N(2)] reveals a trigonal bipyramidal geometry about the metal atom, necessitating the coordination of both phosphorus atoms. The solution NMR spectra are consistent with a C(2)(v)() symmetric complex. Heating the anti complexes results in the clean conversion to the syn complexes, with pyramidal inversion observed at phosphorus. The kinetics of this inversion were studied by (1)H NMR spectroscopy and found to be first-order. Barriers to pyramidal inversion (DeltaG()) were calculated to be 29.1 and 30.1 kcal mol(-)(1) for the aluminum and gallium complexes, respectively; these barriers are approximately 2-3 kcal mol(-)(1) lower than that determined for the metal-free, protonated compounds anti- and syn-H(2)[P(2)N(2)]. It is suggested that the role that the metals play in this inversion, based on the values of DeltaG(), involves the large negative entropies of activation and thus help organize the transition state.

Journal Article↗
PubMed1998

A Preorganized Siderophore: Thermodynamic and Structural Characterization of Alcaligin and Bisucaberin, Microbial Macrocyclic Dihydroxamate Chelating Agents(1).

The iron coordination chemistry of two macrocyclic dihydroxamate siderophores, alcaligin (AG) and bisucaberin (BR), has been investigated thermodynamically and structurally. Alcaligin is a siderophore of freshwater bacteria as well as mammalian pathogens, including the bacterium that causes whooping cough in humans, while bisucaberin, a structural analogue of alcaligin, is produced by marine bacteria. Both alcaligin and bisucaberin form 1:1 ferric complexes (FeL(+)) in acidic conditions and 2:3 ferric complexes (Fe(2)L(3)) at and above neutral pH. The stability constants of these macrocyclic dihydroxamate siderophores differ significantly from that of rhodotorulic acid (RA), a linear dihydroxamate siderophore. Notably, K(FeL) of alcaligin is 32 times greater than that of rhodotorulic acid, while the subsequent stepwise formation constant for Fe(2)L(3) is 3 times less. The Fe(III) complexes of alcaligin are stereospecific; the absolute configuration of the Fe(2)L(3) complex (circular dichroism and X-ray structure) is Lambda. The structure of the Fe(2)L(3) alcaligin complex is a topological alternative to the triple-helicate structure of the rhodotorulic complex Fe(2)(RA)(3). The structures of the free ligand and the bisbidentate ligand in the FeL complex are essentially identical, indicating that alcaligin is highly preorganized for metal ion binding. This explains the difference in K(FeL) between alcaligin and rhodotorulic acid, as well as explaining the monobridged topology of the Fe(2)L(3) alcaligin complex. The protonation constants (log K(a1) and log K(a2)) are 9.42(5) and 8.61(1) for alcaligin and 9.49(2) and 8.76(3) for bisucaberin. The stepwise formation constants of the Fe(III) complexes (log K(ML) and log K(M)()2(L)()3) are 23.5(2) and 17.7(2) for alcaligin and 23.5(5) and 17.2(5) for bisucaberin. The overall formation constants (log beta(230)) of alcaligin and bisucaberin are 64.7(1) and 64.3(1). The solution chemistry of Fe(III) and alcaligin was further investigated at a lower ligand to metal ratio (1:1). At high pH, a novel 2:2 ferric bis-&mgr;-oxo-bridged complex of alcalagin forms (Fe(2)L(2)O(2)(2)(-)) with a log beta(22)(-)(4) of 16.7(2). This species exhibits behavior consistent with an iron bis-&mgr;-oxo complex, including antiferromagnetic coupling. Crystal data: Fe(2)(AG)(3).25H(2)O crystallizes in the orthorhombic space group P2(1)2(1)2(1) with a =13.3374(4) Å, b = 16.1879(5) Å, c = 37.886(1) Å, V = 8179.7(4), Z = 4. For 5512 reflections with F(o)(2) > 3sigma(F(o)(2)) the final R (R(w)) = 0.053(0.068).

Journal Article↗
PubMed2000

Eu(III) macrocyclic complexes promote cleavage of and bind to models for the 5'-cap of mRNA. Effect of pendent group and a second metal ion.

The interaction of three Eu(III) macrocyclic complexes Eu(THED)3+, Eu(ATHC)3+, and Eu(ATHC)3+, and Eu(S-THP)3+ with two 5'-cap model compounds, GpppG and m7GpppG is studied (THED = 1,4,7,10-tetrakis(2-hydroxyethyl)-1,4,7,-10-tetraazacyclododecane, ATHC = 1-(carbamoylmethyl)-4,7,10-tris(2-hydroxyethyl)-1,4,7,10- tetraazacyclododecane, S-THP = 1S,4S,7S,10S-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane). Laser-induced excitation luminescence spectroscopy is used to study the binding of Eu(S-THP)3+ to GpppG (K = 5.9 x 10(4) M-1) and to characterize the Eu(S-THP)-GpppG complex. Both Eu(THED)3+ and Eu(S-THP)3+ bind to m7GpppG as monitored by use of fluorescence spectroscopy with binding constants of 5.9 x 10(3) and 4.4 x 10(4) M-1, respectively. The kinetics of cleavage of GpppG by two macrocyclic complexes is studied. Cleavage of GpppG by Eu(THED)3+ is accelerated by 15-fold in the presence of an equivalent of Zn(NO3)2 at pH 7.3, 37 degrees C, suggesting that two metal ions accelerate the cap cleavage reaction. Eu(ATHC)3+ promotes cleavage of GpppG with a pseudo-first-order rate constant of 2.6 x 10(-5) s-1 at pH 7.3, 37 degrees C, and 0.30 mM complex.

Algorithms↗
PubMed2000

Cis-influence of hydroporphyrin macrocycles on axial ligation equilibria and alkyl exchange reactions of alkylcobalt(III) porphyrin complexes.

Stability constants are reported for the coordination of pyridine and substituted pyridines to the alkylcobalt(III) complexes of octaethylporphyrin (OEP), t-octaethylchlorin (OEC), and ttt-octaethylisobacteriochlorin (OEiBC) in toluene solution. The stability constants correlate with the base strength of the nitrogenous ligand. A cis-influence of the macrocycle saturation level on the stability constants is observed. Stability constants for coordination of a given pyridine ligand to an alkylcobalt(III) complex are roughly 10 times smaller than the stability constants for the corresponding cobalt(II) complex. Analysis of a thermodynamic cycle demonstrates that this leads to decreased stability of the complex with respect to Co-C bond homolysis upon ligand coordination, a "base-on" effect. Alkyl exchange occurs between cobalt complexes of different tetrapyrroles. Equilibrium data establish that the exchange is nonstatistical and that the Co-C bond is stabilized by increasing the saturation of the tetrapyrrole macrocycle.

Alkanes↗
PubMed2001

Synthesis, aggregation, and adsorption phenomena of shape-persistent macrocycles with extraannular polyalkyl substituents.

The synthesis of shape-persistent macrocycles based on the phenyl-ethynyl backbone containing various extraannular alkyl side chains is described. Although compound solubility increases with increasing size of the side groups, decreasing the solvent polarity induces aggregation of the rings by nonspecific interactions. This was investigated by proton NMR spectroscopy. The magnitude of aggregation can be varied by using solvent mixtures of different hexane content, supporting the model of a solvophobic effect. From 1,2,4-trichlorobenzene solution the macrocycle 1c adsorbs at the surface of highly oriented pyrolitic graphite (HOPG). The two-dimensional order of the structure was investigated by scanning tunneling microscopy (STM) revealing the formation of a two-dimensional lattice of p1(2)mm symmetry with lattice parameters A = 3.6 nm, B = 5.7 nm, and Gamma = 74 degrees.

Journal Article↗
PubMed2001

Formation of a phosphorus-phosphorus bond by successive one-electron reductions of a two-phosphinines-containing macrocycle: crystal structures, EPR, and DFT investigations.

Chemical and electrochemical reductions of the macrocycle 1 lead to the formation of a radical monoanion anion [1](*)(-) whose structure has been studied by EPR in liquid and frozen solutions. In accord with experimental (31)P hyperfine tensors, DFT calculations indicate that, in this species, the unpaired electron is mainly localized in a bonding sigma P-P orbital. Clearly, a one-electron bond (2.763 A) was formed between two phosphorus atoms which, in the neutral molecule, were 3.256 A apart (crystal structure). A subsequent reduction of this radical anion gives rise to the dianion [1](2)(-) which could be crystallized by using, in the presence of cryptand, Na naphthalenide as a reductant agent. As shown by the crystal structure, in [1](2)(-), the two phosphinine moieties adopt a phosphacyclohexadienyl structure and are linked by a P-P bond whose length (2.305(2) A) is only slightly longer than a usual P-P bond. When the phosphinine moieties are not incorporated in a macrocycle, no formation of any one-electron P-P bond is observed: thus, one-electron reduction of 3 with Na naphthalenide leads to the EPR spectrum of the ion pair [3](*)(-) Na(+); however, at high concentration, these ion pairs dimerize, and, as shown by the crystal structure of [(3)(2)](2)(-)[(Na(THF)(2))(2)](2+) a P-P bond is formed (2.286(2) A) between two phosphinine rings which adopt a boat-type conformation, the whole edifice being stabilized by two carbon-sodium-phosphorus bridges.

Journal Article↗
PubMed2002

Solvent triggering between conformational states in amphiphilic shape-persistent macrocycles.

The amphiphilic shape-persistent macrocycle 1 containing four phenol-OH groups as polar side groups and four hexyloxy groups as nonpolar side groups in an adaptable arrangement was recrystallized from solvents of different polarity. X-ray crystallography reveals that the conformation of the macrocycle is solvent dependent such that in the pyridine solvate only two of the nonpolar side groups point outward while in the THF solvate all four of them point outward. Moreover, in the latter case the three-dimensional packing leads to the formation of a supramolecular channel structure with a large pore size.

Crystallography, X-Ray↗
PubMed2002

The first example of macrocycles containing butterfly transition metal cluster cores via novel tandem reactions.

A novel type of double butterfly, two mu-CO-containing dianions {[(mu-CO)Fe2(CO)6]2[mu-SCH2(CH2OCH2)nCH2S-mu]}2- (m1, n = 2, 3), has been synthesized from dithiol HSCH2(CH2OCH2)nCH2SH (n = 2, 3), Fe3(CO)12, and Et3N in THF at room temperature. While dianions m1 react in situ with CS2 followed by treatment with dihalide 1,4-(BrCH2)2C6H4 or 1,4-I(CH2)4I to give macrocyclic clusters [mu-SCH2(CH2OCH2)nCH2S-mu](mu-CS2ZCS2-mu)[Fe2(CO)6]2 (1a, n = 2, Z = 1,4-(CH2)2C6H4; 1b, n = 3, Z = (CH2)4), reactions of dianions m1 with (mu-S2)Fe2(CO)6 followed by treatment with dihalide 1,4-I(CH2)4I afford macrocyclic clusters [mu-SCH2(CH2OCH2)nCH2S-mu]{[Fe2(CO)6]2(mu4-S)}2[mu-S(CH2)4S-mu] (2a, n = 2; 2b, n = 3). The crystal structures of 1a and 2b are described.

Journal Article↗
PubMed2002

Atropselective macrocyclization of diaryl ether ring systems: application to the synthesis of vancomycin model systems.

Vancomycin is the last line of defense available in the clinic for treating multidrug-resistant bacterial infections. Vancomycin contains two 16-membered diaryl ether macrocycles, each of which contains a stereogenic axis across the diaryl ether linkage. Since an effective total synthesis of vancomycin requires that these stereogenic axes be formed in a stereoselective manner, we have developed an atropselective variation of the triazene mediated diaryl ether forming reaction. This variation introduced an energetic penalty into the transition state of the undesired atropisomer. This reaction is used to synthesize the C-O-D diaryl ether macrocycle found in vancomycin with high diastereoselectivity (de > 90%), providing the naturally occurring atropisomeric configuration.

Anti-Bacterial Agents↗
PubMed2003

Macrocyclic glycoclusters. Self-aggregation and phosphate-induced agglutination behaviors of calix[4]resorcarene-based quadruple-chain amphiphiles with a huge oligosaccharide pool.

Macrocyclic glycocluster compounds 2n (n = 2-7) with four alkyl (undecyl) chains and eight oligosaccharide moieties on the opposite sides of the calix[4]resorcarene macrocycle are prepared from the reactions of the corresponding octaamine derivative with maltooligosaccharide lactones. Combined evidence from dynamic light scattering (DLS), gel permeation chromatography (GPC), and transmission electron microscopy (TEM) indicates that they form small micelle-like nanoparticles (d congruent with 3 nm) in water. In the presence of Na2HPO4/NaH2PO4, nanoparticles are agglutinated with phosphate ions as a glue to grow in size up to 60-100 nm, as revealed by DLS as well as microscopy (TEM and AFM). The phosphate-induced agglutination processes can be followed by surface plasmon resonance (SPR). Amphiphile 2n is readily immobilized on the hydrophobized sensor chip of SPR to give a closely packed monolayer with oligosaccharide moieties exposed to bulk water. While there is no further adsorption of 2n on the resulting monolayer, this does occur when the latter is pretreated with the phosphate salts, ultimately giving rise to a multilayer upon repeated treatment of the chip with 2n and Na2HPO4/NaH2PO4 in an alternate manner. Kinetic analyses show that the phosphate-mediated inter(saccharide) interactions in terms of rate and affinity are markedly dependent on the oligosaccharide chain lengths (n), becoming more favorable with increasing n's. The novel aggregation and agglutination behaviors observed are discussed in terms of immobilizable and irreversible micelles on the basis of the cone-shaped structure of quadruple-chain amphiphile 2n having a huge saccharide pool and the efficiency of multiple hydrogen bonding therein. The unique intermolecular binding properties of compound 22 and analogues so far reported are reviewed in light of the present finding.

Bridged-Ring Compounds↗
PubMed2003

Stepwise formation of heterobimetallic macrocycles synthesized via the weak-link approach.

A new dissymmetric bis-hemilabile ligand with strong binding phosphorus moieties, weak binding thioether moieties, and weaker binding ether moieties has been synthesized to construct heterobimetallic Rh(I)- and Pd(II)-containing macrocycles. The metals are placed in either the phosphorus/thioether or the phosphorus/ether coordination pocket of the dissymmetric ligand by taking advantage of the stepwise synthetic control offered by the weak-link approach. The weak bonds of these isomeric intermediates are systematically broken through ligand substitution reactions to cleanly and selectively generate a variety of open, macrocyclic architectures.

Journal Article↗
PubMed2003

Efficient macrocyclization of U-turn preorganized peptidomimetics: the role of intramolecular H-bond and solvophobic effects.

Simple peptidomimetic molecules derived from amino acids were reacted with meta- and para-bis(bromomethyl)benzene in acetonitrile to very efficiently yield macrocyclic structures. The cyclization reaction does not require high dilution techniques and seems to be insensitive to the size of the formed macrocycle. The analysis of data obtained by (1)H NMR, single-crystal X-ray diffraction, fluorescence measurements, and molecular mechanics indicate that folded conformations can preorganize the system for an efficient cyclization. The role played by intramolecular hydrogen-bonding and solvophobic effects in the presence of folded conformations is analyzed.

Amides↗
PubMed2003

Total synthesis of (+)-phomactin a using a B-alkyl Suzuki macrocyclization.

A total synthesis of (+)-phomactin A is described using a B-alkyl Suzuki macrocyclization to incorporate the isolated trisubstituted olefin. This macrocyclization was accomplished with the sensitive hydrated furan ring in place. (R)-(+)-pulegone was used to establish the highly substituted cyclohexene core of the molecule.

Cyclization↗