Copper-Based Bioinspired Oxygenation and Glyoxalase-Like Reactivity
Re-engineered, structurally abbreviated models of metalloenzymes may extend their biomimetic functionality to bioinspired reactivity. The oxygenation of external substrates, in particular, remains an important objective of biomimetic and bioinspired catalysis. We report that the reaction of [(Cu(I)T...
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| Veröffentlicht in: | Journal of the American Chemical Society 2002-02, Vol.124 (8), p.1564-1565 |
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| creator | Diaconu, Dana Hu, Zhengbo Gorun, Sergiu M |
| description | Re-engineered, structurally abbreviated models of metalloenzymes may extend their biomimetic functionality to bioinspired reactivity. The oxygenation of external substrates, in particular, remains an important objective of biomimetic and bioinspired catalysis. We report that the reaction of [(Cu(I)TpCF 3 ,CH 3 ) 2 ] with excess acetone in air produces [CuTpCF 3 ,CH 3 )(lactate)] in over 95% yield at ambient conditions, without any noticeable ligand decomposition. This chemically unprecedented one-pot conversion of acetone to lactate occurs as a multistep process in the gluconeogenic pathway catalyzed by P450 isozyme 3a and Ni- or Zn-based glyoxalases. On the basis of the structure of the [CuTpCF 3 ,CH 3 )(lactate)] product and oxygenation experiments using isotopically labeled acetone and water, an inner-sphere oxidation/isomerization mechanism is proposed. |
| doi_str_mv | 10.1021/ja0168458 |
| format | Article |
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The oxygenation of external substrates, in particular, remains an important objective of biomimetic and bioinspired catalysis. We report that the reaction of [(Cu(I)TpCF 3 ,CH 3 ) 2 ] with excess acetone in air produces [CuTpCF 3 ,CH 3 )(lactate)] in over 95% yield at ambient conditions, without any noticeable ligand decomposition. This chemically unprecedented one-pot conversion of acetone to lactate occurs as a multistep process in the gluconeogenic pathway catalyzed by P450 isozyme 3a and Ni- or Zn-based glyoxalases. On the basis of the structure of the [CuTpCF 3 ,CH 3 )(lactate)] product and oxygenation experiments using isotopically labeled acetone and water, an inner-sphere oxidation/isomerization mechanism is proposed.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja0168458</identifier><identifier>PMID: 11853416</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Acetone - chemistry ; Biological and medical sciences ; Chemistry ; Copper - chemistry ; Crystallography, X-Ray ; Exact sciences and technology ; Fundamental and applied biological sciences. Psychology ; Humans ; Kinetics and mechanisms ; Lactoylglutathione Lyase - chemistry ; Lactoylglutathione Lyase - metabolism ; Mechanisms. Catalysis. Electron transfer. Models ; Molecular biophysics ; Molecular Mimicry ; Organic chemistry ; Organometallic Compounds - chemistry ; Oxidation-Reduction ; Physical chemistry in biology ; Reactivity and mechanisms</subject><ispartof>Journal of the American Chemical Society, 2002-02, Vol.124 (8), p.1564-1565</ispartof><rights>Copyright © 2002 American Chemical Society</rights><rights>2002 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a379t-df97c5d2df386dd33f90d7378860425d3d5e4afaf7353d47d2405f616435ef583</citedby><cites>FETCH-LOGICAL-a379t-df97c5d2df386dd33f90d7378860425d3d5e4afaf7353d47d2405f616435ef583</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/ja0168458$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja0168458$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=13503866$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11853416$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Diaconu, Dana</creatorcontrib><creatorcontrib>Hu, Zhengbo</creatorcontrib><creatorcontrib>Gorun, Sergiu M</creatorcontrib><title>Copper-Based Bioinspired Oxygenation and Glyoxalase-Like Reactivity</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Re-engineered, structurally abbreviated models of metalloenzymes may extend their biomimetic functionality to bioinspired reactivity. The oxygenation of external substrates, in particular, remains an important objective of biomimetic and bioinspired catalysis. We report that the reaction of [(Cu(I)TpCF 3 ,CH 3 ) 2 ] with excess acetone in air produces [CuTpCF 3 ,CH 3 )(lactate)] in over 95% yield at ambient conditions, without any noticeable ligand decomposition. This chemically unprecedented one-pot conversion of acetone to lactate occurs as a multistep process in the gluconeogenic pathway catalyzed by P450 isozyme 3a and Ni- or Zn-based glyoxalases. On the basis of the structure of the [CuTpCF 3 ,CH 3 )(lactate)] product and oxygenation experiments using isotopically labeled acetone and water, an inner-sphere oxidation/isomerization mechanism is proposed.</description><subject>Acetone - chemistry</subject><subject>Biological and medical sciences</subject><subject>Chemistry</subject><subject>Copper - chemistry</subject><subject>Crystallography, X-Ray</subject><subject>Exact sciences and technology</subject><subject>Fundamental and applied biological sciences. Psychology</subject><subject>Humans</subject><subject>Kinetics and mechanisms</subject><subject>Lactoylglutathione Lyase - chemistry</subject><subject>Lactoylglutathione Lyase - metabolism</subject><subject>Mechanisms. Catalysis. Electron transfer. Models</subject><subject>Molecular biophysics</subject><subject>Molecular Mimicry</subject><subject>Organic chemistry</subject><subject>Organometallic Compounds - chemistry</subject><subject>Oxidation-Reduction</subject><subject>Physical chemistry in biology</subject><subject>Reactivity and mechanisms</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2002</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0E1LwzAYB_Agis7pwS8guyh4qCZN87KjK06FieIb3sJjk0hm19akle3bm7GxXTwlIT_-PM8foROCLwlOydUUMOEyY3IH9QhLccJIyndRD2OcJkJyeoAOQ5jGZ5ZKso8OCJGMZoT3UJ7XTWN8MoJg9GDkaleFxvl4f5wvvkwFraurAVR6cFsu6jmU0SUT920GzwaK1v26dnGE9iyUwRyvzz56G9-85nfJ5PH2Pr-eJEDFsE20HYqC6VRbKrnWlNoh1oIKKXmci2mqmcnAghWUUZ0JnWaYWU54RpmxTNI-Ol_lNr7-6Uxo1cyFwpQlVKbughIk45yJJbxYwcLXIXhjVePdDPxCEayWjalNY9GerkO7z5nRW7muKIKzNYBQQGk9VIULW0cZjvssXbJyLrRmvvkH_6143JKp16cXRccP-Qd-n6h8mwtFUNO681Xs7p8B_wBkf4yn</recordid><startdate>20020227</startdate><enddate>20020227</enddate><creator>Diaconu, Dana</creator><creator>Hu, Zhengbo</creator><creator>Gorun, Sergiu M</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</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>20020227</creationdate><title>Copper-Based Bioinspired Oxygenation and Glyoxalase-Like Reactivity</title><author>Diaconu, Dana ; Hu, Zhengbo ; Gorun, Sergiu M</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a379t-df97c5d2df386dd33f90d7378860425d3d5e4afaf7353d47d2405f616435ef583</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2002</creationdate><topic>Acetone - chemistry</topic><topic>Biological and medical sciences</topic><topic>Chemistry</topic><topic>Copper - chemistry</topic><topic>Crystallography, X-Ray</topic><topic>Exact sciences and technology</topic><topic>Fundamental and applied biological sciences. Psychology</topic><topic>Humans</topic><topic>Kinetics and mechanisms</topic><topic>Lactoylglutathione Lyase - chemistry</topic><topic>Lactoylglutathione Lyase - metabolism</topic><topic>Mechanisms. Catalysis. Electron transfer. Models</topic><topic>Molecular biophysics</topic><topic>Molecular Mimicry</topic><topic>Organic chemistry</topic><topic>Organometallic Compounds - chemistry</topic><topic>Oxidation-Reduction</topic><topic>Physical chemistry in biology</topic><topic>Reactivity and mechanisms</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Diaconu, Dana</creatorcontrib><creatorcontrib>Hu, Zhengbo</creatorcontrib><creatorcontrib>Gorun, Sergiu M</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</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 the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Diaconu, Dana</au><au>Hu, Zhengbo</au><au>Gorun, Sergiu M</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Copper-Based Bioinspired Oxygenation and Glyoxalase-Like Reactivity</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2002-02-27</date><risdate>2002</risdate><volume>124</volume><issue>8</issue><spage>1564</spage><epage>1565</epage><pages>1564-1565</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>Re-engineered, structurally abbreviated models of metalloenzymes may extend their biomimetic functionality to bioinspired reactivity. The oxygenation of external substrates, in particular, remains an important objective of biomimetic and bioinspired catalysis. We report that the reaction of [(Cu(I)TpCF 3 ,CH 3 ) 2 ] with excess acetone in air produces [CuTpCF 3 ,CH 3 )(lactate)] in over 95% yield at ambient conditions, without any noticeable ligand decomposition. This chemically unprecedented one-pot conversion of acetone to lactate occurs as a multistep process in the gluconeogenic pathway catalyzed by P450 isozyme 3a and Ni- or Zn-based glyoxalases. On the basis of the structure of the [CuTpCF 3 ,CH 3 )(lactate)] product and oxygenation experiments using isotopically labeled acetone and water, an inner-sphere oxidation/isomerization mechanism is proposed.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>11853416</pmid><doi>10.1021/ja0168458</doi><tpages>2</tpages></addata></record> |
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| subjects | Acetone - chemistry Biological and medical sciences Chemistry Copper - chemistry Crystallography, X-Ray Exact sciences and technology Fundamental and applied biological sciences. Psychology Humans Kinetics and mechanisms Lactoylglutathione Lyase - chemistry Lactoylglutathione Lyase - metabolism Mechanisms. Catalysis. Electron transfer. Models Molecular biophysics Molecular Mimicry Organic chemistry Organometallic Compounds - chemistry Oxidation-Reduction Physical chemistry in biology Reactivity and mechanisms |
| title | Copper-Based Bioinspired Oxygenation and Glyoxalase-Like Reactivity |
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