Rational Synthesis of β-Substituted Chlorin Building Blocks
Chlorins bearing synthetic handles at specific sites about the perimeter of the macrocycle constitute valuable building blocks. We previously developed methodology for preparing meso-substituted chlorin building blocks and now present methodology for preparing several complementary β-substituted chl...
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Veröffentlicht in: | Journal of organic chemistry 2000-11, Vol.65 (23), p.7919-7929 |
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creator | Balasubramanian, Thiagarajan Strachan, Jon-Paul Boyle, Paul D Lindsey, Jonathan S |
description | Chlorins bearing synthetic handles at specific sites about the perimeter of the macrocycle constitute valuable building blocks. We previously developed methodology for preparing meso-substituted chlorin building blocks and now present methodology for preparing several complementary β-substituted chlorin building blocks. The chlorins bear one or two β substituents, one meso substituent, a geminal dimethyl group to lock in the chlorin hydrogenation level, and no flanking meso and β substituents. The synthesis involves convergent joining of an Eastern half and a Western half. New routes have been developed to two β-substituted bromo-dipyrromethane monocarbinols (Eastern halves). A new β-substituted Western half was prepared following the method for preparing an unsubstituted Western half (3,3-dimethyl-2,3-dihydrodipyrrin). Chlorin formation is achieved by a two-flask process of acid-catalyzed condensation followed by metal-mediated oxidative cyclization. β-Substituted chlorins have been prepared in 18−24% yield bearing a 4-iodophenyl group at the 8-position, a 4-iodophenyl group or a 4-[2-(trimethylsilyl)ethynyl]phenyl group at the 12-position, and a 4-iodophenyl group and a 4-[2-(trimethylsilyl)ethynyl]phenyl group at diametrically opposed β-positions (2, 12). The latter building block makes possible the stepwise construction of linear multi-chlorin architectures. The chlorins exhibit typical absorption and fluorescence spectra. A systematic shift in the absorption maximum (637−655 nm for the free base chlorins, 606−628 nm for the zinc chlorins) and intensity of the chlorin Q y band (ε up to 79 000 M-1 cm-1) is observed depending on the location of the substituents. The characteristic spectral features and location of substituents in defined positions make these chlorins well suited for a variety of applications in biomimetic and materials chemistry. |
doi_str_mv | 10.1021/jo000913b |
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We previously developed methodology for preparing meso-substituted chlorin building blocks and now present methodology for preparing several complementary β-substituted chlorin building blocks. The chlorins bear one or two β substituents, one meso substituent, a geminal dimethyl group to lock in the chlorin hydrogenation level, and no flanking meso and β substituents. The synthesis involves convergent joining of an Eastern half and a Western half. New routes have been developed to two β-substituted bromo-dipyrromethane monocarbinols (Eastern halves). A new β-substituted Western half was prepared following the method for preparing an unsubstituted Western half (3,3-dimethyl-2,3-dihydrodipyrrin). Chlorin formation is achieved by a two-flask process of acid-catalyzed condensation followed by metal-mediated oxidative cyclization. β-Substituted chlorins have been prepared in 18−24% yield bearing a 4-iodophenyl group at the 8-position, a 4-iodophenyl group or a 4-[2-(trimethylsilyl)ethynyl]phenyl group at the 12-position, and a 4-iodophenyl group and a 4-[2-(trimethylsilyl)ethynyl]phenyl group at diametrically opposed β-positions (2, 12). The latter building block makes possible the stepwise construction of linear multi-chlorin architectures. The chlorins exhibit typical absorption and fluorescence spectra. A systematic shift in the absorption maximum (637−655 nm for the free base chlorins, 606−628 nm for the zinc chlorins) and intensity of the chlorin Q y band (ε up to 79 000 M-1 cm-1) is observed depending on the location of the substituents. The characteristic spectral features and location of substituents in defined positions make these chlorins well suited for a variety of applications in biomimetic and materials chemistry.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo000913b</identifier><identifier>PMID: 11073599</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Fluorescence ; Porphyrins - chemical synthesis</subject><ispartof>Journal of organic chemistry, 2000-11, Vol.65 (23), p.7919-7929</ispartof><rights>Copyright © 2000 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a349t-e7d634c0363fe9da0d9d110ef07d6134ba0bd2ca0918d66b8b5148e4a005ae7f3</citedby><cites>FETCH-LOGICAL-a349t-e7d634c0363fe9da0d9d110ef07d6134ba0bd2ca0918d66b8b5148e4a005ae7f3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jo000913b$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo000913b$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11073599$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Balasubramanian, Thiagarajan</creatorcontrib><creatorcontrib>Strachan, Jon-Paul</creatorcontrib><creatorcontrib>Boyle, Paul D</creatorcontrib><creatorcontrib>Lindsey, Jonathan S</creatorcontrib><title>Rational Synthesis of β-Substituted Chlorin Building Blocks</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>Chlorins bearing synthetic handles at specific sites about the perimeter of the macrocycle constitute valuable building blocks. We previously developed methodology for preparing meso-substituted chlorin building blocks and now present methodology for preparing several complementary β-substituted chlorin building blocks. The chlorins bear one or two β substituents, one meso substituent, a geminal dimethyl group to lock in the chlorin hydrogenation level, and no flanking meso and β substituents. The synthesis involves convergent joining of an Eastern half and a Western half. New routes have been developed to two β-substituted bromo-dipyrromethane monocarbinols (Eastern halves). A new β-substituted Western half was prepared following the method for preparing an unsubstituted Western half (3,3-dimethyl-2,3-dihydrodipyrrin). Chlorin formation is achieved by a two-flask process of acid-catalyzed condensation followed by metal-mediated oxidative cyclization. β-Substituted chlorins have been prepared in 18−24% yield bearing a 4-iodophenyl group at the 8-position, a 4-iodophenyl group or a 4-[2-(trimethylsilyl)ethynyl]phenyl group at the 12-position, and a 4-iodophenyl group and a 4-[2-(trimethylsilyl)ethynyl]phenyl group at diametrically opposed β-positions (2, 12). The latter building block makes possible the stepwise construction of linear multi-chlorin architectures. The chlorins exhibit typical absorption and fluorescence spectra. A systematic shift in the absorption maximum (637−655 nm for the free base chlorins, 606−628 nm for the zinc chlorins) and intensity of the chlorin Q y band (ε up to 79 000 M-1 cm-1) is observed depending on the location of the substituents. The characteristic spectral features and location of substituents in defined positions make these chlorins well suited for a variety of applications in biomimetic and materials chemistry.</description><subject>Fluorescence</subject><subject>Porphyrins - chemical synthesis</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2000</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0LtOwzAUBmALgWgpDLwAygISQ-A4jp1aYqERBaRKXFoWFsuJHeqSxiVOJPpaPAjPhFGqsjCd4Xw6lx-hYwwXGCJ8ubAAwDHJdlAf0whCxiHeRX2AKApJxEgPHTi38AgopfuohzEkhHLeR1fPsjG2kmUwXVfNXDvjAlsE31_htM1cY5q20SpI56WtTRWMWlMqU70Fo9Lm7-4Q7RWydPpoUwfoZXwzS-_CycPtfXo9CSWJeRPqRDES50AYKTRXEhRX_gJdgG9gEmcSMhXl0r8wVIxlw4zieKhj6c-VOinIAJ11c1e1_Wi1a8TSuFyXpay0bZ1IohhTSriH5x3Ma-tcrQuxqs1S1muBQfxGJbZReXuyGdpmS63-5CYbD8IOGNfoz21f1u-CJSShYvY4Fa8snQAec_Hk_WnnZe78nrb2qbp_Fv8Aoyl-zw</recordid><startdate>20001117</startdate><enddate>20001117</enddate><creator>Balasubramanian, Thiagarajan</creator><creator>Strachan, Jon-Paul</creator><creator>Boyle, Paul D</creator><creator>Lindsey, Jonathan S</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20001117</creationdate><title>Rational Synthesis of β-Substituted Chlorin Building Blocks</title><author>Balasubramanian, Thiagarajan ; Strachan, Jon-Paul ; Boyle, Paul D ; Lindsey, Jonathan S</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a349t-e7d634c0363fe9da0d9d110ef07d6134ba0bd2ca0918d66b8b5148e4a005ae7f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2000</creationdate><topic>Fluorescence</topic><topic>Porphyrins - chemical synthesis</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Balasubramanian, Thiagarajan</creatorcontrib><creatorcontrib>Strachan, Jon-Paul</creatorcontrib><creatorcontrib>Boyle, Paul D</creatorcontrib><creatorcontrib>Lindsey, Jonathan S</creatorcontrib><collection>Istex</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Balasubramanian, Thiagarajan</au><au>Strachan, Jon-Paul</au><au>Boyle, Paul D</au><au>Lindsey, Jonathan S</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Rational Synthesis of β-Substituted Chlorin Building Blocks</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2000-11-17</date><risdate>2000</risdate><volume>65</volume><issue>23</issue><spage>7919</spage><epage>7929</epage><pages>7919-7929</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><abstract>Chlorins bearing synthetic handles at specific sites about the perimeter of the macrocycle constitute valuable building blocks. We previously developed methodology for preparing meso-substituted chlorin building blocks and now present methodology for preparing several complementary β-substituted chlorin building blocks. The chlorins bear one or two β substituents, one meso substituent, a geminal dimethyl group to lock in the chlorin hydrogenation level, and no flanking meso and β substituents. The synthesis involves convergent joining of an Eastern half and a Western half. New routes have been developed to two β-substituted bromo-dipyrromethane monocarbinols (Eastern halves). A new β-substituted Western half was prepared following the method for preparing an unsubstituted Western half (3,3-dimethyl-2,3-dihydrodipyrrin). Chlorin formation is achieved by a two-flask process of acid-catalyzed condensation followed by metal-mediated oxidative cyclization. β-Substituted chlorins have been prepared in 18−24% yield bearing a 4-iodophenyl group at the 8-position, a 4-iodophenyl group or a 4-[2-(trimethylsilyl)ethynyl]phenyl group at the 12-position, and a 4-iodophenyl group and a 4-[2-(trimethylsilyl)ethynyl]phenyl group at diametrically opposed β-positions (2, 12). The latter building block makes possible the stepwise construction of linear multi-chlorin architectures. The chlorins exhibit typical absorption and fluorescence spectra. A systematic shift in the absorption maximum (637−655 nm for the free base chlorins, 606−628 nm for the zinc chlorins) and intensity of the chlorin Q y band (ε up to 79 000 M-1 cm-1) is observed depending on the location of the substituents. The characteristic spectral features and location of substituents in defined positions make these chlorins well suited for a variety of applications in biomimetic and materials chemistry.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>11073599</pmid><doi>10.1021/jo000913b</doi><tpages>11</tpages></addata></record> |
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title | Rational Synthesis of β-Substituted Chlorin Building Blocks |
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