Novel Porphyrinoids for Chemistry and Medicine by Biomimetic Syntheses

Abstract

The cowr picture shows ii schematic representation of the arrangement in a crystal that resembles a tartan. I t i s the expected structure for the 1 :1 adduct formed betwcen ;I tetracationic cyclophane and ferrocene (green). The cyclophane was designed t o permit recognition both in an external and internal fashion. Indeed, the cyclophaiic Ibrms sheets and channels in the solid state through external recognition betwen i1.s conhtituent components. The cyclophane also complexes substrates such ;IS fcrrocenc ~i t h i n i t s cavitj predicted, whilst retaining the ability to form highly structured three-dimensional arrays. in common with the free cyclophane. Stoddart et d . LIX I .3-bis(2-bromoethoxy)ben~eiie (red) and bipyridine (blue) as building blocks t o ahsemble the desired tetracationic cyclophane. More about the free cycloplianc and i t s 1 : 1 fei-rocene adduct --esamples of "molecular mosaics"-are reported on p. 1802 fl'. REVIEWS ContentsExtremel) high intensity pigments with extinction coefficients up to 50 times larger than that o f the industrially important pigment indigo are the red t g n -. the violet 26 n-. and the blue 34n-porphyrins shown below. For these porphyrins a linear relationship exists between the wavelength of the most intense Soret band and the number o f 7t electrons in the iiiacro le. With syntheses based o n those in nature. :I Iai-gc niimbcr of expanded. bridged. inverted. and N-substituted porphyriii derivat i b e z is accessible with interesting properties for chemical and medicinal applicat I on \ .

Expanded Porphyrins: Intriguing Structures, Electronic Properties, and Reactivities

“…The systematic nomenclature of porphyrin analogues, as proposed by Franck and Nonn, [9] is useful for expanded porphyrins. In this nomenclature, an name of an expanded porphyrin consists of three parts: 1) a core name that indicates the number of pyrrole subunits in such a way as to use pentaphyrin 2, hexaphyrin 3, and heptaphyrin 4 for expanded porphyrins consisting of five, six, and seven pyrrolic subunits, respectively, 2) the number in the square-bracketed prefix indicates the number of p electrons in the effective macrocyclic conjugation, and 3) the numbers in the roundbracketed suffix indicate the numbers of bridging carbon atoms between the constitutional pyrrole groups, starting from the largest unit.…”

One‐Pot Synthesis of Indene‐Expanded Porphyrins

“…18 10 5 m À1 to 1.79 10 5 m À1 at 543 nm) upon protonation with DCA. With regard to the related bisvinylogous porphyrins, Franck and Nonn [19] have previously attributed this increased absorptivity to increased symmetry in the system with all four nitrogen atoms being protonated.…”

“…resembles that described for bisvinylogous porphyrins. [19] That is, the absorbance intensity of E.P. simply increases (from 1.…”

Spectroscopic Studies of Newly Synthesized Steroidal Pyrroles

“…1 They are vital building blocks for the construction of bio-active molecules such as porphyrins, alkaloids and co-enzymes. 2 The biological importance of pyrrole and its derivatives cannot be overemphasized because they have shown to possess extensive biological activities and pharmacological properties such as antimicrobial, analgesics, ionotropic, antitumor, anti-inflammatory, and antiallergic. [3][4][5][6][7][8][9][10] These have also been employed as P38kinase, 11 prolyl -4-hydroxylase, 12 poly(ADP-ribose) polymerase inhibitors, 13 estrogen receptor β-selective ligands, 14 AT1-selective angiotensin II receptor antagonists, 15 and minor groove recognition elements.…”