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The crystal structure of (R,R)-4-bromo-2-{4-[4-bromo-1-(4-toluenesulfonyl)-1H-pyrrol-2-yl]-1,3-dinitrobutan-2-yl}-1-(4-toluenesulfonyl)-1H-pyrrole (1, C26H24Br2N4O8S2) is presented. The title compound was isolated in suitable yield as a by-product in our synthesis of geminal-dimethyl hydrodipyrrins. We observe an unforeseen enantiomeric resolution both in the bulk sample and the crystal of 1, with distinct C--H--O (Cmethyi--H--Onitro, Csp3--H--Osulfonyi) interactions observed in the enantiomers present, along with other interactions, namely C5-pyrrolyl--H-«-Osulfonyl, forming a polymer along the crystallographic caxis direction. Whiist pyrroiic fragments are weii documented in the iiterature, little data is found surrounding the 1,3-dinitrobutane scaffold. [ABSTRACT FROM AUTHOR]

The crystal structure of (R,R)-4-bromo-2-{4-[4-bromo-1-(4-toluenesulfonyl)-1H-pyrrol-2-yl]-1,3-dinitrobutan-2-yl|-1-(4-toluenesulfonyl)-1H-pyrrole (1, C26H24Br2N4O8S2) is presented. The title compound was isolated in suitable yield as a by-product in our synthesis of geminal-dimethyl hydrodipyrrins. We observe an unforeseen enantiomeric resolution both in the bulk sample and the crystal of 1, with distinct C--H⋯O (Cmethyl--H⋯Onitro, C...--H⋯Osulfonyl) interactions observed in the enantiomers present, along with other interactions, namely C5-pyrrolyl--H⋯Osulfonyl, forming a polymer along the crystallographic c-axis direction. Whilst pyrrolic fragments are well documented in the literature, little data is found surrounding the 1,3-dinitrobutane scaffold. [ABSTRACT FROM AUTHOR]

The nucleophilic substitution of aromatic moieties (SNAr) has been known for over 150 years and found wide use for the functionalization of (hetero)aromatic systems. Currently, several "types" of SNAr reactions have been established and notably the area of porphyrinoid macrocycles has seen many uses thereof. Herein, we detail the SNAr reactions of seven types of porphyrinoids with differing number and type of pyrrole units: subporphyrins, norcorroles, corroles, porphyrins, azuliporphyrins, N‐confused porphyrins, and phthalocyanines. For each we analyze the substitution dependent upon: a) the type of nucleophile and b) the site of substitution (α, β, or meso). Along with this we evaluate this route as a synthetic strategy for the generation of unsymmetrical porphyrinoids. Distinct trends can be identified for each type of porphyrinoid discussed, regardless of nucleophile. The use of nucleophilic substitution on porphyrinoids is found to often be a cost‐effective procedure with the ability to yield complex substituent patterns, which can be conducted in non‐anhydrous solvents with easily accessible simple porphyrinoids. [ABSTRACT FROM AUTHOR]

The crystal structures of three S -(pyridin-2-yl) benzo-thio-esters with varying para -phenyl substituents are presented, namely, S -(pyridin-2-yl) 4-nitro-benzo-thio-ate ( 1 , C 12 H 8 N 2 O 3 S), S -(pyridin-2-yl) 4-methyl-benzo-thio-ate ( 2 , C 13 H 11 NO 2 S) and S -(pyridin-2-yl) 4-meth-oxy-benzo-thio-ate ( 3 , C 13 H 11 NO 2 S). This class of compounds are used in the mono-acyl-ation of pyrrolic species to yield multifunctional tetra-pyrroles. The structures presented herein are the first of their compound class. The dominant inter-actions present in this series are π-π stacking and C-H⋯O inter-actions, and as the para -phenyl motif changes from electron withdrawing (NO 2 , 1 ) to electron donating (OCH 3 , 3 ), changes are observed in the inter-actions present in the crystal packing, from predominant π-π stacking in 1 to exclusively C-H⋯O/N inter-actions (C ar-yl -H⋯O carbon-yl , C-H⋯O meth-oxy and C ar-yl -H⋯N pyridine ) in 3 ., (© Sample et al. 2023.)

The crystal structures of three inter-mediate compounds in the synthesis of 8-bromo-2,3,4,5-tetra-hydro-1,3,3-tri-methyl-dipyrrin are reported; 4-bromo-2-formyl-1-tosyl-1 H -pyrrole, C 12 H 10 BrNO 3 S, ( E )-4-bromo-2-(2-nitro-vin-yl)-1-tosyl-1 H -pyrrole, C 13 H 11 BrN 2 O 4 S, and 6-(4-bromo-1-tosyl-pyrrol-2-yl)-4,4-dimethyl-5-nitro-hexan-2-one, C 19 H 23 BrN 2 O 5 S. The compounds show multitudinous inter-molecular C-H⋯O inter-actions, with bond distances and angle consistent in the series and within expectations, as well as varied packing types. The merits of collecting data beyond the standard resolution usually reported for small mol-ecules are discussed., (© Kingsbury et al. 2021.)

The nucleophilic substitution of aromatic moieties (S N Ar) has been known for over 150 years and found wide use for the functionalization of (hetero)aromatic systems. Currently, several "types" of S N Ar reactions have been established and notably the area of porphyrinoid macrocycles has seen many uses thereof. Herein, we detail the S N Ar reactions of seven types of porphyrinoids with differing number and type of pyrrole units: subporphyrins, norcorroles, corroles, porphyrins, azuliporphyrins, N-confused porphyrins, and phthalocyanines. For each we analyze the substitution dependent upon: a) the type of nucleophile and b) the site of substitution (α, β, or meso). Along with this we evaluate this route as a synthetic strategy for the generation of unsymmetrical porphyrinoids. Distinct trends can be identified for each type of porphyrinoid discussed, regardless of nucleophile. The use of nucleophilic substitution on porphyrinoids is found to often be a cost-effective procedure with the ability to yield complex substituent patterns, which can be conducted in non-anhydrous solvents with easily accessible simple porphyrinoids., (© 2020 The Authors. European Journal of Organic Chemistry published by Wiley‐VCH GmbH.)