Soluble Poly(diacetylene)s Using the Perfluorophenyl−Phenyl Motif as a Supramolecular Synthon

A series of diacetylene monomers with benzoyl, 4-hexylbenzoyl, 4-dodecylbenzoyl, and perfluorobenzoyl substituents were synthesized and investigated with respect to their crystal structures and polymerizability. In the absence of perfluorophenyl−phenyl interactions, the crystal structures of related alkylated and nonalkylated derivatives were substantially different and dominated by the phase segregation between the alkylated side chains and the diaryl-substituted diacetylene cores. By contrast, the perfluorophenyl−phenyl interactions served as a reliable supramolecular synthon in that they persisted in the crystal structures of different alkylated and nonalkylated derivatives. The packing of the diacetylene functions was appropriate for a topochemical polymerization in these cases, and the perfluorophenyl−phenyl interaction determined the polymerization direction. As a result, soluble alternating diacetylene copolymers were obtained which were further characterized with solution phase methods

Soluble Poly(diacetylene)s Using the Perfluorophenyl−Phenyl Motif as a Supramolecular Synthon

A series of diacetylene monomers with benzoyl, 4-hexylbenzoyl, 4-dodecylbenzoyl, and perfluorobenzoyl substituents were synthesized and investigated with respect to their crystal structures and polymerizability. In the absence of perfluorophenyl−phenyl interactions, the crystal structures of related alkylated and nonalkylated derivatives were substantially different and dominated by the phase segregation between the alkylated side chains and the diaryl-substituted diacetylene cores. By contrast, the perfluorophenyl−phenyl interactions served as a reliable supramolecular synthon in that they persisted in the crystal structures of different alkylated and nonalkylated derivatives. The packing of the diacetylene functions was appropriate for a topochemical polymerization in these cases, and the perfluorophenyl−phenyl interaction determined the polymerization direction. As a result, soluble alternating diacetylene copolymers were obtained which were further characterized with solution phase methods

Soluble Poly(diacetylene)s Using the Perfluorophenyl−Phenyl Motif as a Supramolecular Synthon

A series of diacetylene monomers with benzoyl, 4-hexylbenzoyl, 4-dodecylbenzoyl, and perfluorobenzoyl substituents were synthesized and investigated with respect to their crystal structures and polymerizability. In the absence of perfluorophenyl−phenyl interactions, the crystal structures of related alkylated and nonalkylated derivatives were substantially different and dominated by the phase segregation between the alkylated side chains and the diaryl-substituted diacetylene cores. By contrast, the perfluorophenyl−phenyl interactions served as a reliable supramolecular synthon in that they persisted in the crystal structures of different alkylated and nonalkylated derivatives. The packing of the diacetylene functions was appropriate for a topochemical polymerization in these cases, and the perfluorophenyl−phenyl interaction determined the polymerization direction. As a result, soluble alternating diacetylene copolymers were obtained which were further characterized with solution phase methods

Soluble Poly(diacetylene)s Using the Perfluorophenyl−Phenyl Motif as a Supramolecular Synthon

A series of diacetylene monomers with benzoyl, 4-hexylbenzoyl, 4-dodecylbenzoyl, and perfluorobenzoyl substituents were synthesized and investigated with respect to their crystal structures and polymerizability. In the absence of perfluorophenyl−phenyl interactions, the crystal structures of related alkylated and nonalkylated derivatives were substantially different and dominated by the phase segregation between the alkylated side chains and the diaryl-substituted diacetylene cores. By contrast, the perfluorophenyl−phenyl interactions served as a reliable supramolecular synthon in that they persisted in the crystal structures of different alkylated and nonalkylated derivatives. The packing of the diacetylene functions was appropriate for a topochemical polymerization in these cases, and the perfluorophenyl−phenyl interaction determined the polymerization direction. As a result, soluble alternating diacetylene copolymers were obtained which were further characterized with solution phase methods

Soluble Poly(diacetylene)s Using the Perfluorophenyl−Phenyl Motif as a Supramolecular Synthon

A series of diacetylene monomers with benzoyl, 4-hexylbenzoyl, 4-dodecylbenzoyl, and perfluorobenzoyl substituents were synthesized and investigated with respect to their crystal structures and polymerizability. In the absence of perfluorophenyl−phenyl interactions, the crystal structures of related alkylated and nonalkylated derivatives were substantially different and dominated by the phase segregation between the alkylated side chains and the diaryl-substituted diacetylene cores. By contrast, the perfluorophenyl−phenyl interactions served as a reliable supramolecular synthon in that they persisted in the crystal structures of different alkylated and nonalkylated derivatives. The packing of the diacetylene functions was appropriate for a topochemical polymerization in these cases, and the perfluorophenyl−phenyl interaction determined the polymerization direction. As a result, soluble alternating diacetylene copolymers were obtained which were further characterized with solution phase methods

C₆₀ Pyrrolidine Bis-carboxylic Acid Derivative as a Versatile Precursor for Biocompatible Fullerenes

A C₆₀ Prato derivative with bis-^<i>t</i>Bu ester was prepared as a stable and convenient scaffold for the development of fullerene derivatives such as water-soluble C₆₀–PEG conjugates, fulleropeptides <i>via</i> solid phase synthesis, and bis-functionalized C₆₀

Soluble Poly(diacetylene)s Using the Perfluorophenyl−Phenyl Motif as a Supramolecular Synthon

A series of diacetylene monomers with benzoyl, 4-hexylbenzoyl, 4-dodecylbenzoyl, and perfluorobenzoyl substituents were synthesized and investigated with respect to their crystal structures and polymerizability. In the absence of perfluorophenyl−phenyl interactions, the crystal structures of related alkylated and nonalkylated derivatives were substantially different and dominated by the phase segregation between the alkylated side chains and the diaryl-substituted diacetylene cores. By contrast, the perfluorophenyl−phenyl interactions served as a reliable supramolecular synthon in that they persisted in the crystal structures of different alkylated and nonalkylated derivatives. The packing of the diacetylene functions was appropriate for a topochemical polymerization in these cases, and the perfluorophenyl−phenyl interaction determined the polymerization direction. As a result, soluble alternating diacetylene copolymers were obtained which were further characterized with solution phase methods

Soluble Poly(diacetylene)s Using the Perfluorophenyl−Phenyl Motif as a Supramolecular Synthon

A series of diacetylene monomers with benzoyl, 4-hexylbenzoyl, 4-dodecylbenzoyl, and perfluorobenzoyl substituents were synthesized and investigated with respect to their crystal structures and polymerizability. In the absence of perfluorophenyl−phenyl interactions, the crystal structures of related alkylated and nonalkylated derivatives were substantially different and dominated by the phase segregation between the alkylated side chains and the diaryl-substituted diacetylene cores. By contrast, the perfluorophenyl−phenyl interactions served as a reliable supramolecular synthon in that they persisted in the crystal structures of different alkylated and nonalkylated derivatives. The packing of the diacetylene functions was appropriate for a topochemical polymerization in these cases, and the perfluorophenyl−phenyl interaction determined the polymerization direction. As a result, soluble alternating diacetylene copolymers were obtained which were further characterized with solution phase methods

Tolerance of Base Pair Size and Shape in Postlesion DNA Synthesis

The influence of base pair size and shape on the fidelity of DNA polymerase-mediated extension past lesion-containing mispairs was examined. Primer extension analysis was performed with synthetic nucleosides paired opposite the pro-mutagenic DNA lesion <i>O</i>⁶-benzylguanine (<i>O</i>⁶-BnG). These data indicate that the error-prone DNA polymerase IV (Dpo4) inefficiently extended past the larger Peri:<i>O</i>⁶-BnG base pair, and in contrast, error-free extension was observed for the smaller BIM:<i>O</i>⁶<i>-</i>BnG base pair. Steady-state kinetic analysis revealed that Dpo4 catalytic efficiency was strongly influenced by the primer:template base pair. Compared to the C:G pair, a 1.9- and 79 000-fold reduction in Dpo4 efficiency was observed for terminal C:<i>O</i>⁶-BnG and BIM:G base pairs respectively. These results demonstrate the impact of geometrical size and shape on polymerase-mediated mispair extension

Stereoselective Synthesis of 12,13-Cyclopropyl-Epothilone B and Side-Chain-Modified Variants

A general strategy has been devised for the stereoselective synthesis of 12,13-cyclopropyl-epothilone B and side-chain-modified variants thereof, which relies on late stage introduction of the heterocycle through Wittig olefination of ketone 14. Formation of the macrocycle was achieved through RCM-based ring closure and introduction of the cyclopropane moiety involved a highly selective Charette cyclopropanation of allylic alcohol 7