A <i>trans</i>-AB-Bacteriochlorin Building Block

Synthetic bacteriochlorins are of interest for fundamental studies in photochemistry because of their strong absorption in the near-infrared spectral region and close similarity with natural bacteriochlorophylls. A de novo route to 5-methoxybacteriochlorins entails self-condensation of a dihydrodipyrrin–acetal, which in turn is prepared from a 2-(2-nitroethyl)­pyrrole species and an α,β-unsaturated ketone–acetal (e.g., 1,1-dimethoxy-4-methylpent-3-en-2-one). Here, four new results are reported concerning the synthesis of substituted bacteriochlorins. First, a new, scalable route to 1,1-dimethoxy-4-methylpent-3-en-2-one removes a significant previous impediment to the overall route. Second, the new route was employed to gain access to new α,β-unsaturated ketones and corresponding dihydrodipyrrins bearing alternative substituents in place of the dimethoxy unit. Third, a dihydrodipyrrin bearing a 1,3-dioxolan-2-yl moiety afforded the bacteriochlorin (30% yield) containing a 2-hydroxyethoxy substituent at the 5-position. Fourth, subsequent bromination proceeded regioselectively at the 15-position to give a trans-(5,15)-AB-bacteriochlorin building block. The linear 5,15-substitution pattern is attractive for a number of molecular designs. The results taken together afford deeper understanding of the scope and limitations of the de novo route and also advance the capabilities for tailoring synthetic bacteriochlorins

Synthesis and Photochemical Properties of 12-Substituted versus 13-Substituted Chlorins

Understanding the effects of substituents on natural photosynthetic pigments is essential for the rational design of artificial photosynthetic systems. The long-wavelength absorption of chlorins derives from a transition that encompasses rings A and C, which includes the 2,3- and 12,13-positions, respectively. Chlorophylls bear a 3-vinyl group and a 13-keto group, as well as a full complement of substituents at the other β-pyrrole sites. Prior studies of sparsely substituted synthetic chlorins to probe the effects of substituents yielded 3,13-substituted chlorins that contain a geminal dimethyl group in the pyrroline ring (for stability) and a mesityl group at the 10-position. Attempts to prepare analogous chlorins lacking the 10-mesityl substituent encountered unexpected difficulties during construction of the Eastern half precursor (8,9-dibromo-1-formyldipyrromethane) to the 13-bromochlorin. Direct bromination of 1-formyldipyrromethane with 2 mol equiv of NBS at −78 °C led to an isomeric mixture of the desired 8,9-dibromodipyrromethane (minor) and the unexpected 7,9-dibromodipyrromethane (major). Hence, a new rational route was developed for the synthesis of 8,9-dibromo-1-formyldipyrromethane that entailed (i) InCl3-catalyzed condensation of 4-bromo-2-(hydroxymethyl)pyrrole and pyrrole to give the 8-bromodipyrromethane, (ii) 1-formylation, and (iii) 9-bromination. Two new substituted chlorins carrying auxochromes at the 3- and 13-positions were synthesized. The photophysical and redox properties of the 13-substituted chlorins were compared with those of isomeric 12-substituted chlorins, synthesized previously via a 7,9-dibromo-1-formyldipyrromethane. Such studies (static absorption and fluorescence spectroscopy, time-resolved fluorescence spectroscopy, electrochemistry of the zinc chelates, and density functional theoretical calculations) reveal only very slight differences between the isomeric 12- and 13-substituted chlorins

Synthesis and Photochemical Properties of 12-Substituted versus 13-Substituted Chlorins

Understanding the effects of substituents on natural photosynthetic pigments is essential for the rational design of artificial photosynthetic systems. The long-wavelength absorption of chlorins derives from a transition that encompasses rings A and C, which includes the 2,3- and 12,13-positions, respectively. Chlorophylls bear a 3-vinyl group and a 13-keto group, as well as a full complement of substituents at the other β-pyrrole sites. Prior studies of sparsely substituted synthetic chlorins to probe the effects of substituents yielded 3,13-substituted chlorins that contain a geminal dimethyl group in the pyrroline ring (for stability) and a mesityl group at the 10-position. Attempts to prepare analogous chlorins lacking the 10-mesityl substituent encountered unexpected difficulties during construction of the Eastern half precursor (8,9-dibromo-1-formyldipyrromethane) to the 13-bromochlorin. Direct bromination of 1-formyldipyrromethane with 2 mol equiv of NBS at −78 °C led to an isomeric mixture of the desired 8,9-dibromodipyrromethane (minor) and the unexpected 7,9-dibromodipyrromethane (major). Hence, a new rational route was developed for the synthesis of 8,9-dibromo-1-formyldipyrromethane that entailed (i) InCl3-catalyzed condensation of 4-bromo-2-(hydroxymethyl)pyrrole and pyrrole to give the 8-bromodipyrromethane, (ii) 1-formylation, and (iii) 9-bromination. Two new substituted chlorins carrying auxochromes at the 3- and 13-positions were synthesized. The photophysical and redox properties of the 13-substituted chlorins were compared with those of isomeric 12-substituted chlorins, synthesized previously via a 7,9-dibromo-1-formyldipyrromethane. Such studies (static absorption and fluorescence spectroscopy, time-resolved fluorescence spectroscopy, electrochemistry of the zinc chelates, and density functional theoretical calculations) reveal only very slight differences between the isomeric 12- and 13-substituted chlorins

Synthesis and Photochemical Properties of 12-Substituted versus 13-Substituted Chlorins

Understanding the effects of substituents on natural photosynthetic pigments is essential for the rational design of artificial photosynthetic systems. The long-wavelength absorption of chlorins derives from a transition that encompasses rings A and C, which includes the 2,3- and 12,13-positions, respectively. Chlorophylls bear a 3-vinyl group and a 13-keto group, as well as a full complement of substituents at the other β-pyrrole sites. Prior studies of sparsely substituted synthetic chlorins to probe the effects of substituents yielded 3,13-substituted chlorins that contain a geminal dimethyl group in the pyrroline ring (for stability) and a mesityl group at the 10-position. Attempts to prepare analogous chlorins lacking the 10-mesityl substituent encountered unexpected difficulties during construction of the Eastern half precursor (8,9-dibromo-1-formyldipyrromethane) to the 13-bromochlorin. Direct bromination of 1-formyldipyrromethane with 2 mol equiv of NBS at −78 °C led to an isomeric mixture of the desired 8,9-dibromodipyrromethane (minor) and the unexpected 7,9-dibromodipyrromethane (major). Hence, a new rational route was developed for the synthesis of 8,9-dibromo-1-formyldipyrromethane that entailed (i) InCl3-catalyzed condensation of 4-bromo-2-(hydroxymethyl)pyrrole and pyrrole to give the 8-bromodipyrromethane, (ii) 1-formylation, and (iii) 9-bromination. Two new substituted chlorins carrying auxochromes at the 3- and 13-positions were synthesized. The photophysical and redox properties of the 13-substituted chlorins were compared with those of isomeric 12-substituted chlorins, synthesized previously via a 7,9-dibromo-1-formyldipyrromethane. Such studies (static absorption and fluorescence spectroscopy, time-resolved fluorescence spectroscopy, electrochemistry of the zinc chelates, and density functional theoretical calculations) reveal only very slight differences between the isomeric 12- and 13-substituted chlorins

Synthesis and Photochemical Properties of 12-Substituted versus 13-Substituted Chlorins

Understanding the effects of substituents on natural photosynthetic pigments is essential for the rational design of artificial photosynthetic systems. The long-wavelength absorption of chlorins derives from a transition that encompasses rings A and C, which includes the 2,3- and 12,13-positions, respectively. Chlorophylls bear a 3-vinyl group and a 13-keto group, as well as a full complement of substituents at the other β-pyrrole sites. Prior studies of sparsely substituted synthetic chlorins to probe the effects of substituents yielded 3,13-substituted chlorins that contain a geminal dimethyl group in the pyrroline ring (for stability) and a mesityl group at the 10-position. Attempts to prepare analogous chlorins lacking the 10-mesityl substituent encountered unexpected difficulties during construction of the Eastern half precursor (8,9-dibromo-1-formyldipyrromethane) to the 13-bromochlorin. Direct bromination of 1-formyldipyrromethane with 2 mol equiv of NBS at −78 °C led to an isomeric mixture of the desired 8,9-dibromodipyrromethane (minor) and the unexpected 7,9-dibromodipyrromethane (major). Hence, a new rational route was developed for the synthesis of 8,9-dibromo-1-formyldipyrromethane that entailed (i) InCl3-catalyzed condensation of 4-bromo-2-(hydroxymethyl)pyrrole and pyrrole to give the 8-bromodipyrromethane, (ii) 1-formylation, and (iii) 9-bromination. Two new substituted chlorins carrying auxochromes at the 3- and 13-positions were synthesized. The photophysical and redox properties of the 13-substituted chlorins were compared with those of isomeric 12-substituted chlorins, synthesized previously via a 7,9-dibromo-1-formyldipyrromethane. Such studies (static absorption and fluorescence spectroscopy, time-resolved fluorescence spectroscopy, electrochemistry of the zinc chelates, and density functional theoretical calculations) reveal only very slight differences between the isomeric 12- and 13-substituted chlorins

Synthesis and Photochemical Properties of 12-Substituted versus 13-Substituted Chlorins

Understanding the effects of substituents on natural photosynthetic pigments is essential for the rational design of artificial photosynthetic systems. The long-wavelength absorption of chlorins derives from a transition that encompasses rings A and C, which includes the 2,3- and 12,13-positions, respectively. Chlorophylls bear a 3-vinyl group and a 13-keto group, as well as a full complement of substituents at the other β-pyrrole sites. Prior studies of sparsely substituted synthetic chlorins to probe the effects of substituents yielded 3,13-substituted chlorins that contain a geminal dimethyl group in the pyrroline ring (for stability) and a mesityl group at the 10-position. Attempts to prepare analogous chlorins lacking the 10-mesityl substituent encountered unexpected difficulties during construction of the Eastern half precursor (8,9-dibromo-1-formyldipyrromethane) to the 13-bromochlorin. Direct bromination of 1-formyldipyrromethane with 2 mol equiv of NBS at −78 °C led to an isomeric mixture of the desired 8,9-dibromodipyrromethane (minor) and the unexpected 7,9-dibromodipyrromethane (major). Hence, a new rational route was developed for the synthesis of 8,9-dibromo-1-formyldipyrromethane that entailed (i) InCl3-catalyzed condensation of 4-bromo-2-(hydroxymethyl)pyrrole and pyrrole to give the 8-bromodipyrromethane, (ii) 1-formylation, and (iii) 9-bromination. Two new substituted chlorins carrying auxochromes at the 3- and 13-positions were synthesized. The photophysical and redox properties of the 13-substituted chlorins were compared with those of isomeric 12-substituted chlorins, synthesized previously via a 7,9-dibromo-1-formyldipyrromethane. Such studies (static absorption and fluorescence spectroscopy, time-resolved fluorescence spectroscopy, electrochemistry of the zinc chelates, and density functional theoretical calculations) reveal only very slight differences between the isomeric 12- and 13-substituted chlorins

Synthesis and Photochemical Properties of 12-Substituted versus 13-Substituted Chlorins

Understanding the effects of substituents on natural photosynthetic pigments is essential for the rational design of artificial photosynthetic systems. The long-wavelength absorption of chlorins derives from a transition that encompasses rings A and C, which includes the 2,3- and 12,13-positions, respectively. Chlorophylls bear a 3-vinyl group and a 13-keto group, as well as a full complement of substituents at the other β-pyrrole sites. Prior studies of sparsely substituted synthetic chlorins to probe the effects of substituents yielded 3,13-substituted chlorins that contain a geminal dimethyl group in the pyrroline ring (for stability) and a mesityl group at the 10-position. Attempts to prepare analogous chlorins lacking the 10-mesityl substituent encountered unexpected difficulties during construction of the Eastern half precursor (8,9-dibromo-1-formyldipyrromethane) to the 13-bromochlorin. Direct bromination of 1-formyldipyrromethane with 2 mol equiv of NBS at −78 °C led to an isomeric mixture of the desired 8,9-dibromodipyrromethane (minor) and the unexpected 7,9-dibromodipyrromethane (major). Hence, a new rational route was developed for the synthesis of 8,9-dibromo-1-formyldipyrromethane that entailed (i) InCl3-catalyzed condensation of 4-bromo-2-(hydroxymethyl)pyrrole and pyrrole to give the 8-bromodipyrromethane, (ii) 1-formylation, and (iii) 9-bromination. Two new substituted chlorins carrying auxochromes at the 3- and 13-positions were synthesized. The photophysical and redox properties of the 13-substituted chlorins were compared with those of isomeric 12-substituted chlorins, synthesized previously via a 7,9-dibromo-1-formyldipyrromethane. Such studies (static absorption and fluorescence spectroscopy, time-resolved fluorescence spectroscopy, electrochemistry of the zinc chelates, and density functional theoretical calculations) reveal only very slight differences between the isomeric 12- and 13-substituted chlorins