Synthesis and Studies of Fused Benzo-Benzisapphyrins.

A series of rare examples of fused benzo-benzisapphyrins were synthesized readily by (3 + 2) condensation of benzodipyrrole-derived diol and para-benzitripyrrane in the presence of 0.5 equiv of TFA in CH2Cl2 under inert atmosphere conditions accompanied by DDQ oxidation in open air. The crude compounds were separated by basic alumina column chromatography and afforded pure fused benzo-benzisapphyrins in 20-22% yields. The fused sapphyrins were characterized in detail by high-resolution mass spectrometry (HRMS) and one-dimensional (1D) and two-dimensional (2D) NMR spectroscopy. The 1H NMR spectra recorded at both 298 and at 233 K clearly exhibited the presence of a strong diatropic ring current in benzo-benzisapphyrins, and the macrocycles are of aromatic nature. The DFT-optimized structure of benzo-benzisapphyrin revealed that the macrocycle was planar to a great extent due to the rigid structure of the dibenzopyrrole moiety, and the NICS(0) value of -11.2 ppm supports the aromatic nature of macrocycles. The absorption spectra of benzo-benzisapphyrins showed three weak Q bands approximately in the region of 650-900 nm and a strong Soret band at 480 nm, along with a shoulder band at ∼510 nm. The diprotonated derivative generated by the addition of excess TFA to the benzo-benzisapphyrin macrocycle exhibited bathochromically shifted absorption bands compared to the free base macrocycle.

Dibenzoylbenzodipyrroles: Key Precursors for the Synthesis of Fused meso-Aryl Sapphyrins.

A simple strategy has been developed for the synthesis of α,α'-dibenzoylbenzodipyrroles, which are key synthons for the synthesis of fused porphyrinoids. α,α'-Dibenzoylbenzodipyrroles were characterized by high-resolution mass spectrometry (HRMS), NMR, and X-ray crystallography. To show the use of α,α'-dibenzoylbenzodipyrrole, we synthesized five different fused meso-aryl sapphyrins under acid-catalyzed reaction conditions. α,α'-Dibenzoylbenzodipyrrole was reduced to diol and condensed with five different tripyrranes such as aza, oxa, thia, selena, and telluratripyrranes under mild acid-catalyzed conditions to afford fused meso-aryl sapphyrins in 15-18% yields. One-dimensional (1D) and two-dimensional (2D) NMR studies revealed that in fused sapphyrins, the furan ring in oxabenzosapphyrin and the pyrrole ring in benzosapphyrin, which are present opposite to the benzodipyrrole moiety, attained ring inversion (inverted sapphyrins), whereas the selenophene ring in selenabenzosapphyrin and the tellurophene ring in tellurabenzosapphyrin did not show ring inversion (normal sapphyrins). However, thiabenzosapphyrin exhibits both normal and inverted conformations in different ratios. All fused sapphyrins showed typical aromatic absorption features; however, the absorption features of normal fused sapphyrins are different from the inverted fused sapphyrins. Redox studies indicate that normal fused sapphyrins are difficult to oxidize but easier to reduce compared to inverted fused sapphyrins. Density functional theory (DFT) studies support the experimental observations.

Facile Synthesis of Fused Oxasapphyrins.

A simple rapid synthetic route is developed to synthesize new fused meso-aryl oxasapphyrins in 8-10% yield using easily accessible 3-benzoylpyrrole as the key precursor. The method involves McMurry coupling of 3-benzoylpyrrole to obtain an E/Z mixture of dipyrroethene, which was subjected to benzoylation followed by NaBH4 reduction to afford dipyrroethene diol in situ that was then condensed with 16-oxatripyrrane under mild acid-catalyzed conditions to afford fused oxasapphyrins.