Synthesis of meso-Triaryl 22-Oxanorroles

Abstract

Norroles are isomers of corroles containing a direct pyrrole N–pyrrole C link instead of a pyrrole C–pyrrole C link of corroles. 22-Oxanorroles are core-modified norroles in which one of the pyrroles is replaced with a furan ring. A straightforward route is adopted to synthesize the first examples of aromatic meso-triaryl-22-oxanorroles containing a pyrrole N–pyrrole α-C direct bond in 4–7% yields by condensing 16-oxatripyrrane and (1H-pyrrol-3-yl)­(p-tolyl)­methanol in CH2Cl2 under mild acid-catalyzed conditions followed by oxidation with DDQ.

Panchromatic and Perturbed Absorption Spectral Features and Multiredox Properties of Dicyanovinyl- and Dicyanobutadienyl-Appended Cobalt Corroles

“…The introduction of DCV unit(s) and DCBD unit(s) at 3- or 3,17-positions resulted in huge red-shifts in the longest wavelength band for mono- (46–60 nm) and disubstituted (75–80 nm) corroles compared to their respective precursors due to the extended π-conjugation and strong electron-withdrawing effect of these chromophores that resulted in splitting, broadening, and weakening of the Soret-like bands, and strengthening of the Q-band intensity probably might be the result of the intramolecular charge transfer (ICT) feature from the macrocyclic ring to various β-substituents . The observed spectral features are unique and similar to recently reported oxanorroles, oxabenzonorroles, triarylbiphenylcorrole, and cobalt hypercorroles. ,− Surprisingly, AMN-(Cor)­Co , (MN) 2 -(Cor)­Co , and A 2 MN 2 -(Cor)­Co exhibited almost twice as high molar absorptivity in the Q band compared to Soret band(s) as that of their precursors. To the best of our knowledge, we are reporting the Q-band intensity two times higher than the Soret band for the first time.…”

Organometallic chemistry confined within a porphyrin-like framework

“…Also, the oxanorrole derivative has been recently synthesised. 276 S121-4 and S121-5 accommodate copper(III), which seems to be a natural central cation for the trianionic cavity. 275 The insertion proceeds from copper(II) acetate and gives stable S122-1 (Scheme 122) and S123-1 (Scheme 123).…”

Enantioselective Direct Synthesis of C3-Hydroxyalkylated Pyrrole via an Amine-Catalyzed Aldol/Paal–Knorr Reaction Sequence

“…Next, 1-naphthaldehyde 3p as a bulkier aldehyde was tested under the standard conditions to initially furnish 5up (60%, 99:1 er), which upon subsequent IBX oxidation yielded 1-propyl-3-(1-naphthoyl)­pyrroles 9 (83%); thus, a two-pot quick synthesis of pyrrole-based cannabinoid has been developed (Scheme ii), despite the loss of chirality during oxidation. This method provides easy access to heteroarylmethanols/3-acylpyrroles, which are attractive substrates for N-confused calix[5]­pyrroles and meso -triaryl 22-oxanorroles . Additionally, 1-[aryl­(1 H -pyrrol-3-yl)­methyl]-1 H -imidazole 10 (55% yield) was obtained as a racemic mixture when 5af was reacted with 1,1′-carbonyldiimidazole (CDI) (Scheme iii), and similar units were recently established as antiprotozoal agents …”

“…This method provides easy access to heteroarylmethanols/3-acylpyrroles, which are attractive substrates for N-confused calix [5]pyrroles 28 and meso-triaryl 22-oxanorroles. 29 Additionally, 1-[aryl(1H-pyrrol-3-yl)methyl]-1H-imidazole 10 (55% yield) was obtained as a racemic mixture when 5af was reacted with 1,1′-carbonyldiimidazole (CDI) (Scheme 2iii), and similar units were recently established as antiprotozoal agents. 30 In summary, we have developed the first metal-free enantioselective synthesis of C3-hydroxyalkylated N-alkyl/Ar/ H-pyrroles from aqueous succinaldehyde, acceptor carbonyls, and primary amines in a sequential multicomponent fashion.…”