Synthesis and characterization of water-soluble amino fullerene derivatives

[formula: see text] A series of amino-substituted methanofullerene derivatives were prepared by mono-, tris-, and hexa-Bingel-Hirsch reactions using an N-protected malonate derivative. Upon scission of the protecting groups, the e,e,e-tris- and octahedral Th hexa-methano amino fullerenes were found to be among the most water-soluble fullerene derivatives yet prepared. 3He NMR data on corresponding adducts of 3He/C60 helped verify the assigned structures. UV spectral studies confirmed the influence of aggregation on solubility of these adducts in water.     

Alkaloid-fullerene systems through photocycloaddition reactions

The photocycloaddition of tertiary amines to ?60fullerene (C(60)) is an interesting and useful reaction. We wished to extend the applications of this type of reaction through an investigation of the photoaddition of alkaloids to C(60) for the purpose of synthesizing novel and complex photoadducts that are difficult to obtain by usual methods. Irradiation of tazettine (2) or gramine (3) with C(60) in toluene leads to formation of one monoadduct (6 or 7), whereas scandine (1a) or 10-hydroxyscandine (1b) reacts with C(60) photochemically to give two products, the expected ?6,6 monoadduct (5a, 5b) and a new type of monoadduct with a bis-?6, 6 closed structure (4a, 4b). These new structures were characterized by UV-vis, FT-IR, (1)H NMR, (13)C NMR, (1)H-(1)H COSY, ROESY, HMQC (heteronuclear multiple-quantum coherence), and HMBC (heteronuclear multiple-bond connectivity) spectroscopy. The techniques of time-of-flight secondary ion MS (TOF-SIMS) and field desorption MS (FD-MS) were used for the mass determination. (3)He NMR analysis of the product mixture from photoaddition of 1a to C(60) containing a (3)He atom ((3)He@C(60)) led to two peaks at -9.091 and -11.090 ppm relative to gaseous (3)He, consistent with formation of a ?6, 6-closed monoadduct and a bis-?6,6 closed adduct. Presumably, the bis-?6, 6 closed adducts are formed by an intramolecular ?2 + 2 cycloaddition of the vinyl group to the adjacent 6,6-ring junction of C(60) after the initial photocycloaddition.     

Reversible Diels-Alder addition to fullerenes: a study of equilibria using (3)He NMR spectroscopy.

3He NMR spectroscopy has been used to study the equilibria of Diels-Alder additions of 9,10-dimethyl anthracene (DMA) to (3)He@C(60) and (3)He@C(70). Spectra of a series of equilibrium mixtures showed peaks for the isomeric adducts. One monoadduct, six bis-adducts, eleven tris-adducts, and ten tetrakis-adducts of DMA to C(60) were seen. One monoadduct and three bis-adducts of C(70) were detected. Equilibrium constants were found for these reactions and values for DeltaG, DeltaH, and DeltaS were obtained.     

Preparation and photophysical studies of a fluorous phase-soluble fullerene derivative

We report the first synthesis of a well-characterized "Teflon ponytail" fullerene adduct (3) via the Hirsch-Bingel reaction with a malonate bearing two perfluorinated alkyl chains. This C3 tris-adduct shows excellent solubility in perfluorinated solvents, such as FC-72 and FC-75. Compound 3 was found to be an efficient sensitizer for singlet oxygen formation in fluorous media, which has potential in biphasic systems and in photobiology.     

New concepts for regio- and stereoselective bis- and triscyclopropanations of C60

The synthesis of isomerically multiple adducts of C(60) with a defined three-dimensional structure is still one of the most challenging tasks of exohedral fullerene chemistry. The inherent regioselectivity of successive additions of addends such as malonates to the fullerene's [6,6]-double bonds is only moderate. In most cases difficult-to-isolate mixtures of regioisomers are obtained. The regioselectivity can be significantly improved if multifunctional addends able to undergo two or more additions are allowed to react with C(60). Preorganization and minimization of strain energy within the addend skeleton reduce the number of sterically allowed addition patterns. Improved concepts for highly regio- and stereoselective bis- and triscyclopropanations of C(60) are described. Two examples of the bisadditions with complete regioselectivity leading to trans-2- and cis-2 are presented. Here, the two malonate binding sites are linked by rigid tetraphenylporphyrin and calix-[4]-arene spacers. Selective trisadditions were achieved with the easy-to-synthesize and easy-to-modify tripodal addends 5-7, where the malonates are held together by a focal aryl moiety. Another very elegant approach for bis- and trisadditions involves cyclo-[n]-alkylmalonates. Selection between addition patterns with and without rotational axes is possible by choosing the right combinations of the flexible alkyl chains connecting the malonates. If alkyl chains of identical lengths are used bis- and trisadducts such as 19-21 and 25 with rotational symmetry are formed with high regioselectivity. These addition patterns are avoided if cyclo-[n]-malonates containing alkyl chains of different lengths are employed. In this case adducts such as 26 and 27 with C(s)-symmetry are formed. The use of the chiral cyclo-[3]-malonate 28 allows for the regio- and stereoselective synthesis of the enantiomerically pure e,e,e-trisadducts 29 and 30 containing an inherently chiral addition pattern with C(3)-symmetry.     

New hybrid [2]catenanes based on a 4,4'-bipyridinium ligand

The self-assembly-mediated synthesis of metallomacrocycles 4a and 4b from (en)M(NO3)2 (M = Pd, Pt) and bipyridinium ligand 3 is described. The reaction is templated by disodium p-phenyldiacetic dicarboxylate, which is inserted into the macrocyclic cavity. Similarly, the self-assembly process between ligand 3, (en)M(NO3)2 (M = Pd, Pt), and the macrocyclic polyether 6 resulted in the formation of hybrid catenanes 7a and 7b. In the [2]catenanes, the circumrotation of the macrocyclic polyether through the cavity of the metallocycle is slow on the 1H NMR time scale.     

Iron Sulfido Derivatives of the Fullerenes C(60) and C(70)

Toluene solutions of C(60) react upon UV irradiation with Fe(2)S(2)(CO)(6) to give C(60)[S(2)Fe(2)(CO)(6)](n)() where n = 1-6. C(60)[S(2)Fe(2)(CO)(6)](n)() where n = 1-3 have been isolated and characterized. Crystallographic studies of C(60)S(2)Fe(2)(CO)(6) show that the S-S bond of the Fe(2) reagent is cleaved to give a dithiolate with idealized C(2)(v)() symmetry. The addition occurred at a 6,6 fusion, and the metrical details show that the Fe(2) portion of the molecule resembles C(2)H(4)S(2)Fe(2)(CO)(6). IR spectroscopic measurements indicate that the Fe(2)(CO)(6) subunits in the multiple-addition species (n > 1) interact only weakly. UV-vis spectra of the adducts show a shift to shorter wavelength with addition of each S(2)Fe(2)(CO)(6) unit. Photoaddition of the phosphine complex Fe(2)S(2)(CO)(5)(PPh(3)) to C(60) gave C(60)[S(2)Fe(2)(CO)(5)(PPh(3))](n)(), where n = 1-3. (31)P{(1)H} NMR studies show that the double adduct consists of multiple isomers. Photoaddition of Fe(2)S(2)(CO)(6) to C(70) gave a series of adducts C(70)[S(2)Fe(2)(CO)(6)](n)() where n = 1-4. HPLC analyses show one, four, and three isomers for the adducts, respectively.     

One-pot regioselective synthesis and X-ray crystal structure of a stable [60]fullerene trisadduct with the e(edge),e(face),trans-1 addition pattern

The Bingel functionalisation of C(60) with a structurally novel tether equipped with three reactive malonate groups afforded a C(2v)-symmetrical e(edge),e(face),trans-1 trisadduct in a complete regioselective manner and in an excellent yield of 65%. The [60]fullerene trisadduct showed pronounced ability to crystallise and gave X-ray quality single crystals for analysis.     

Optically Active Macrocyclic cis‐3 Bis‐Adducts of C60: Regio‐ and Stereoselective Synthesis,Exciton Chirality Coupling,and Determination of the Absolute Configuration,and First Observation of Exciton Coupling between Fullerene Chromophores in a Chiral Environment

A series of optically active cis‐3 bis‐adducts, such as (R,R,^fC)‐ 16 (Scheme 6), was obtained regio‐ and diastereoselectively by Bingel macrocyclization of C₆₀ with bis‐malonates, which contain optically active tethers derived from 1,2‐diols. The absolute configuration of the inherently chiral addition pattern in cis‐3 bis‐adducts had previously been determined by comparison of calculated and experimental circular dichroism (CD) spectra. Full confirmation of these earlier assignments was now obtained by an independent method based on semiempirical AM1 (`Austin Model 1') and OM2 (`Orthogonalization Method 2') calculations combined with ¹H‐NMR spectroscopy. It was found computationally that bis‐malonates [CHR(OCOCH₂COOEt)]₂, which contain (R,R)‐ or (S,S)‐butane‐2,3‐diol derivatives as optically active tethers, preferentially form out‐out cis‐3 bis‐adducts of C₆₀ as a single diastereoisomer in which the alkyl groups R adopt a gauche conformation, while the two glycolic H‐atoms are in an antiperiplanar (ap) and the ester linkages to the fullerene in a gauche relationship (Figs. 2 and 5). In contrast, in the less favorable diastereoisomer, which should not form, the alkyl groups R adopt an ap and the H‐atoms a gauche conformation, while the ester bridges to the fullerene remain, for geometric reasons, locked in a gauche conformation. According to the OM2 calculations, the geometry of the fully staggered tether in the free bis‐malonates closely resembles the conformation of the tether fragment in the bis‐adducts formed. These computational predictions were confirmed experimentally by the measurement of the coupling constant between the vicinal glycolic H‐atoms in the ¹H‐NMR spectrum. For (R,R,^fC)‐ 16 , ³J(H,H) was determined as 7.9 Hz, in agreement with the ap conformation, and, in combination with the calculations, this allowed assignment of the ^fC‐configuration to the inherently chiral addition pattern. This conformational analysis was further supported by the regio‐ and diastereoselective synthesis of cis‐3 bis‐adducts from bis‐malonates, including tethers derived from cyclic glycol units with a fixed gauche conformation of the alkyl residues R at the glycolic C‐atoms. Thus, a bis‐malonate of (R,R)‐cyclohexane‐1,2‐diol provided exclusively cis‐3 bis‐adduct (R,R,^fC)‐ 20 in 32% yield (Scheme 7). Incorporation of a tether derived from methyl 4,6‐O,O‐benzylidene‐α‐D ‐glucopyranoside into the bis‐malonate and Bingel macrocyclization diastereoselectively produced the cis‐3 stereoisomer (α,D ,^fA)‐ 22 (Scheme 8) as the only macrocyclic bis‐adduct. If the geometry of the alkyl groups R at the glycolic C‐atoms of the tether component deviates from a gauche relationship, as in the case of tethers derived from exo cis‐ and trans‐norbornane‐2,3‐diol or from trans‐cyclopentane‐1,2‐diol, hardly any macrocyclic product is formed (Schemes 5 and 9). The absolute configurations of the various optically active cis‐3 bis‐adducts were also assigned by comparison of their CD spectra, which are dominated by the chiroptical contributions of the inherently chiral fullerene chromophore (Figs. 1, 3, and 4). A strong chiral exciton coupling was observed for optically active macrocyclic cis‐3 bis‐adducts of C₆₀ with two appended 4‐(dimethylamino)benzoate ((S,S,^fC)‐ 26 ; Fig. 6) or meso‐tetraphenylporphyrin ((R,R,^fC)‐ 28 ; Fig. 7) chromophores. Chiral exciton coupling between two fullerene chromophores was observed for the first time in the CD spectrum of the threitol‐bridged bis‐fullerene (R,R)‐ 35 (Fig. 9).     

Light‐Controlled Regioselective Synthesis of Fullerene Bis‐Adducts

Multi‐functionalization and isomer‐purity of fullerenes are crucial tasks for the development of their chemistry in various fields. In both current main approaches—tether‐directed covalent functionalization and supramolecular masks—the control of regioselectivity requires multi‐step synthetic procedures to prepare the desired tether or mask. Herein, we describe light‐responsive tethers, containing an azobenzene photoswitch and two malonate groups, in the double cyclopropanation of [60]fullerene. The formation of the bis‐adducts and their spectroscopic and photochemical properties, as well as the effect of azobenzene photoswitching on the regiochemistry of the bis‐addition, have been studied. The behavior of the tethers depends on the geometry of the connection between the photoactive core and the malonate moieties. One tether lead to a strikingly different adduct distribution for the E and Z isomers, indicating that the covalent bis‐functionalization of C₆₀ can be controlled by light.     

Adducts of phenoxathiin and thianthrene cation radicals with alkenes and cycloalkenes

Phenoxathiin cation radical perchlorate (PO.+ClO4(-)) added stereospecifically to cyclopentene, cyclohexene, cycloheptene, and 1,5-cyclooctadiene to give 1,2-bis(5-phenoxathiiniumyl)cycloalkane diperchlorates (4-7) in good yield. The diaxial configuration of the PO+ groups was confirmed with X-ray crystallography. Unlike additions of thianthrene cation radical perchlorate (Th.+ClO4(-)) to these cycloalkenes, no evidence for formation of monoadducts was found in the reactions of PO.+ClO4(-). This difference is discussed. Addition of Th.+ClO4(-) to five trans alkenes (2-butene, 2-pentene, 4-methyl-2-pentene, 3-octene, 5-decene) and four cis alkenes (2-pentene, 2-hexene, 2-heptene, 5-decene) gave in each case a mixture of mono- and bisadducts in which the configuration of the alkene was retained. Thus, cis alkenes gave erythro monoadducts and threo bisadducts, whereas trans alkenes gave threo monoadducts and erythro bisadducts. In these additions to alkenes, cis alkenes gave predominantly bisadducts, while trans alkenes (except for trans-2-butene) gave predominantly monoadducts. This difference is explained. 1,2-Bis(5-phenoxathiiniumyl)cycloalkanes (4-7) and 1,2-bis(5-thianthreniumyl)cycloalkanes underwent fast elimination reactions on activated alumina forming, respectively, 1-(5-phenoxathiiniumyl)cycloalkenes (8-11) and 1-(5-thianthreniumyl)cycloalkenes (12-16). Among adducts of Th.+ClO4(-) and alkenes, monoadducts underwent fast ring opening on alumina to give (5-thianthreniumyl)alkenes, while bisadducts underwent fast eliminations of H+ and thianthrene (Th) to give (5-thianthreniumyl)alkenes also. Ring opening of monoadducts was a stereospecific reaction in which the configuration of the original alkene was retained. Thus, erythro monoadducts (from cis alkenes) gave (E)-(5-thianthreniumyl)alkenes and threo monoadducts (from trans alkenes) gave (Z)-(5-thianthreniumyl)alkenes. Among bisadducts, elimination of a proton and Th occurred and was more complex, giving both (E)- and (Z)-(5-thianthreniumyl)alkenes. These results are explained. Configurations of adducts and (5-thianthreniumyl)alkenes were deduced with the aid of X-ray crystallography and (1)H and (13)C NMR spectroscopy. In the NMR spectra of (E)- and (Z)-(5-thianthreniumyl)alkenes, the alkenyl proton of Z isomers always appeared at a lower field (0.8-1.0 ppm) than that of E isomers.     

A highly regioselective approach to multiple adducts of C60 governed by strain minimization of macrocyclic malonate addends

New macrocyclic malonates 2-5 have been prepared by reaction of malonyl dichloride with alkanediols. Reactions of these cyclo-[n]-alkylmalonates with C60 are highly regioselective. The macrocycles containing identical alkyl spacers selectively form bis- and trisadducts of C60 with rotational symmetry. The addition pattern of the regioselectively formed oligoadducts is determined by the size of the alkyl spacer within the macrocyclic malonate. A variety of bis-, tris-, tetra-, and hexaadducts have been synthesized to show the scope of this approach. "Exotic" addition patterns such as trans-4,trans-4,trans-4, which has been synthesized and completely characterized for the first time, are also accessible by this method. The regioselectivity is ruled by the even distribution of the strain within the macrocyclic malonates containing spacer alkane chains of identical lengths: addition patterns with rotational symmetry provide exactly identical distances of the malonate oxygen atoms and are thus exclusively formed by this method. In contrast, when macrocycles with two different alkyl spacer lengths are used, such as 9 and 10, the reaction exclusively yields C(s)-symmetric bisadducts.     

Hexakis‐Adducts of [60]Fullerene with Different Addition Patterns: Templated Synthesis,Physical Properties,and Chemical Reactivity

Representatives of two classes of hexakis‐adducts of C₆₀ were prepared by templated synthesis strategies. Compound 8 with a dipyridylmethano addend in a pseudo‐octahedral addition pattern was obtained by DMA‐templated addition (DMA=9,10‐dimethylanthracene; Scheme 1) and served as the starting material for the first supramolecular fullerene dimer 2 . Hexakis‐adduct 12 also possesses a pseudo‐octahedral addition pattern and was obtained by a sequence of tether‐directed remote functionalization, tether removal, and regioselective bis‐functionalization (Scheme 2). With its two diethynylmethano addends in trans‐1 position, it is a precursor for fascinating new oligomers and polymers that feature C₆₀ moieties as part of the polymeric backbone (Fig. 1). With the residual fullerene π‐electron chromophore reduced to a `cubic cyclophane'‐type sub‐structure (Fig. 4), and for steric reasons, 8 and 12 no longer display electrophilic reactivity. As a representative of the second class of hexakis‐adducts, (±)‐ 1 , which features six addends in a distinct helical array along an equatorial belt, was prepared by a route that involved two sequential tether‐directed remote functionalization steps (Schemes 3 and 5). In compound (±)‐ 1 , π‐electron conjugation between the two unsubstituted poles of the carbon sphere is maintained via two (E)‐stilbene‐like bridges (Fig. 4). As a result, (±)‐ 1 features very different chemical reactivity and physical properties when compared to hexakis‐adducts with a pseudo‐octahedral addition pattern. Its reduction under cyclic voltammetric conditions is greatly facilitated (by 570 mV), and it readily undergoes additional, electronically favored Bingel additions at the two sterically well‐accessible central polar 6‐6 bonds under formation of heptakis‐ and octakis‐adducts, (±)‐ 30 and (±)‐ 31 , respectively (Scheme 6). The different extent of the residual π‐electron delocalization in the fullerene sphere is also reflected in the optical properties of the two types of hexakis‐adducts. Whereas 8 and 12 are bright‐yellow (end‐absorption around 450 nm), compound (±)‐ 1 is shiny‐red, with an end‐absorption around 600 nm. This study once more demonstrates the power of templated functionalization strategies in fullerene chemistry, providing addition patterns that are not accessible by stepwise synthetic approaches.     

3He NMR study of (3)He@C(60)H(6) and (3)He@C(70)H(2)(-)(10)

The (3)He NMR of (3)He@C(60)H(6), (3)He@C(70)H(2), (3)He@C(70)H(4), (3)He@C(70)H(8), and (3)He@C(70)H(10) have been investigated. A new, unidentified C(60)H(6) isomer has been found by using (3)He NMR. (3)He@C(70)H(10) shows the most downfield-shifted (3)He NMR resonance among the neutral C(70) derivatives.     

3He NMR as a sensitive probe of fullerene reactivity: [2 + 2] photocycloaddition of 3-methyl-2-cyclohexenone to C70

The [2 + 2] photoadditions of 3-methyl-2-cyclohexenone to C70 and 3He@C70 have been studied by a combination of HPLC chromatography and FAB-MS, as well as IR and 1H and 3He NMR spectroscopies. The total yield of the mixture of monoadducts was 55% (67% on the basis of the recovered C70). The use of 3He NMR was especially powerful in determining the regioselectivity of the photoaddition reaction of enone to C70. Results of the 3He NMR experiments conducted on the product mixture implicate the two [6,6] bonds closest to the poles of the fullerene (C1-C2 and C5-C6) in the photoaddition process. This reaction mode is analogous to that of most thermal addition reactions to C70. Separation and characterization of the product mixture shows that eight distinct monoadducts are formed in the photoaddition, namely, the four diastereomeric adducts to the C1-C2 and C5-C6 bonds of the C70 cage, each consisting of cis- and trans-fused isomers in a ratio of 2:3. The major mode of photoaddition, accounting for 65% of the product mixture, involves addition to the C1-C2 bond of the ovoid fullerene. Mechanistic implications of these findings are discussed.     

Introduction of bis-discotic and bis-calamitic mesogenic addends to C 60

The synthesis and characterization of four C 60 Bingel cyclopropanation adducts incorporating bis-biphenylene (three adducts) and bis-triphenylene (one adduct) moieties are described. The thermal analysis (POM and DSC) of these materials reveals that they are not liquid crystalline. However, two of the precursor bis-biphenylene malonate esters possess monotropic mesophases. Furthermore, each of the corresponding C 60 adducts is miscible in the melts of the precursor malonate ester, and at low dopings, retains the liquid crystalline monotropic mesophases of the precursor.     

The addition of amides to group 14 (di)-metallenes

The addition of a series of primary and secondary amides to the group 14 (di)metallenes Mes(2)Si=SiMes(2), Mes(2)Ge=GeMes(2) and (Me(3)Si)(2)Si=C(OSiMe(3))R, where R = t-Bu or R = 1-Ad, was examined. In general, the addition of primary and N-methyl amides gave amide adducts whereas the addition of N-phenyl amides gave imidate adducts. The regiochemistry of the additions was highly dependent upon the substituent bonded to the amide nitrogen. We propose that the formation of the adducts proceeds by way of a zwitterionic intermediate. The reactivity of tetramesityldigermene towards amides is used to predict the structure of the amide adducts formed on the Ge(100)-2 × 1 surface.     

Thermally stable gold(I) beta-diketiminate complexes

The synthesis and X-ray structures of gold(I) adducts supported by beta-diketiminates have been reported. {[HC{(H)C(2,4,6-Br(3)C(6)H(2))N}(2)]Au}(2) and {[HC{(H)C(Dipp)N}(2)]Au}(2) [Dipp = 2,6-(i-Pr)(2)C(6)H(3)] are easily isolable solids and feature 12-membered macrocyclic ring structures. beta-Diketiminate ligands adopt a W-shaped conformation. Gold atoms are bonded to the nitrogen atoms in a linear fashion. (1)H NMR signals corresponding to the protons at the beta-diketiminate ligand beta-C position of the gold adducts appear at a notably high downfield region.     

Stereoselective synthesis of stannyl enones via palladium-catalyzed and free radical hydrostannation of alkynyl ketones with trineophyltin hydride

A study on the addition of trineophyltin hydride (1) to alkynones under free radical (AIBN and Et3B) and palladium-catalyzed [(PPh3)2PdCl2] conditions is reported. The results obtained indicate that the addition of 1 to eight ynones catalyzed by bis(triphenylphosphine)palladium(II) chloride led in all cases to addition products in very high yields (80-96%). These additions take place with excellent regio- and stereochemistry, leading to the alpha adducts as major products in seven out of the eight cases studied. Also the E adducts, resulting from a syn attack, were the only (seven cases) or the predominant (one case) products. The radical hydrostannations initiated by AIBN of ynones 2-5 with 1 led to addition products in good yields (60-88%); with the more hindered ketones 6 and 7-9 the yields obtained were lower. The radical additions initiated by triethylboron to ynones 2-6 follow a similar pattern but with lower yields; no addition products in the hydrostannation of ynones 7-9 were detected. The new acyl-substituted vinylstannanes, owing to their greater stability compared with that of their tributyl- and trimethylstannyl analogues, can be purified by column chromatography using neutral alumina (in all cases) or silica gel 60 (in most cases) as adsorbents. Full 1H, 13C, and 119Sn NMR data are given.     

Ammonium ion binding with pyridine-containing crown ethers

Dipyrido[24]crown-8 (DP24C8) has been synthesized and shown to form [2]pseudorotaxanes spontaneously with dibenzylammonium ions. These complexes, which have been demonstrated by (1)H NMR spectroscopy to form faster in solution than when the macrocyclic polyether is dibenzo[24]crown-8 (DB24C8), are also stronger than their DB24C8 counterparts. One of the [2]pseudorotaxanes has been used to construct a [2]rotaxane (see above) comprising a dumbbell-shaped component based on a dibenzylammonium ion which is encircled by a DP24C8 macrocycle and terminated by (triphenylphosphonium)methyl stoppers.