Synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and spermidines. Elucidation of the stereochemical course of putrescine aminopropyltransferase (spermidine synthase)
The stereochemical course of enzyme-catalyzed aminopropyl transfer has been investigated. The stereospecific synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and several chirally deuteriated spermidine (-)-camphanamide derivatives has allowed the elucidation of aminopropyl...
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| Veröffentlicht in: | J. Am. Chem. Soc.; (United States) 1988-08, Vol.110 (17), p.5791-5799 |
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| container_title | J. Am. Chem. Soc.; (United States) |
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| creator | Orr, Gary R Danz, Deborah W Pontoni, Gabriele Prabhakaran, P. C Gould, Steven J Coward, James K |
| description | The stereochemical course of enzyme-catalyzed aminopropyl transfer has been investigated. The stereospecific synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and several chirally deuteriated spermidine (-)-camphanamide derivatives has allowed the elucidation of aminopropyltransferase stereochemistry by using /sup 1/H NMR techniques. Putrescine aminopropyltransferase (spermidine synthase) isolated from Eschierchia coli catalyzed the synthesis of chirally deuteriated spermidines from 1,4-diaminobutane (putrescine) and chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines. Derivatization of the biosynthetic spermidines to 1,8-bis(Boc)spermidine (-)-camphanamides and comparison of their /sup 1/H NMR spectra with those of the synthetic standards permits determination of the absolute configuration of the biosynthetic products. The results show that the reaction catalyzed by E. coli spermidine synthase proceeds with inversion of configuration at the methylene carbon undergoing nucleophilic attack by putrescine. These data support a single-displacement mechanism proceeding via a ternary complex of enzyme and both substrates. 42 references, 5 figures. |
| doi_str_mv | 10.1021/ja00225a034 |
| format | Article |
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Elucidation of the stereochemical course of putrescine aminopropyltransferase (spermidine synthase)</title><source>ACS Publications</source><creator>Orr, Gary R ; Danz, Deborah W ; Pontoni, Gabriele ; Prabhakaran, P. C ; Gould, Steven J ; Coward, James K</creator><creatorcontrib>Orr, Gary R ; Danz, Deborah W ; Pontoni, Gabriele ; Prabhakaran, P. C ; Gould, Steven J ; Coward, James K ; Rensselaer Polytechnic Institute, Troy, NY (USA)</creatorcontrib><description>The stereochemical course of enzyme-catalyzed aminopropyl transfer has been investigated. The stereospecific synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and several chirally deuteriated spermidine (-)-camphanamide derivatives has allowed the elucidation of aminopropyltransferase stereochemistry by using /sup 1/H NMR techniques. Putrescine aminopropyltransferase (spermidine synthase) isolated from Eschierchia coli catalyzed the synthesis of chirally deuteriated spermidines from 1,4-diaminobutane (putrescine) and chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines. Derivatization of the biosynthetic spermidines to 1,8-bis(Boc)spermidine (-)-camphanamides and comparison of their /sup 1/H NMR spectra with those of the synthetic standards permits determination of the absolute configuration of the biosynthetic products. The results show that the reaction catalyzed by E. coli spermidine synthase proceeds with inversion of configuration at the methylene carbon undergoing nucleophilic attack by putrescine. These data support a single-displacement mechanism proceeding via a ternary complex of enzyme and both substrates. 42 references, 5 figures.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja00225a034</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>400201 - Chemical & Physicochemical Properties ; 400202 - Isotope Effects, Isotope Exchange, & Isotope Separation ; Aliphatic compounds ; ALKANES ; AMINES ; Chemistry ; DATA ; DEUTERIUM ; Exact sciences and technology ; EXPERIMENTAL DATA ; HYDROCARBONS ; HYDROGEN ISOTOPES ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; ISOTOPES ; LABELLED COMPOUNDS ; LIGHT NUCLEI ; NUCLEI ; NUMERICAL DATA ; ODD-ODD NUCLEI ; Organic chemistry ; ORGANIC COMPOUNDS ; Preparations and properties ; SPERMIDINE ; STABLE ISOTOPES ; SYNTHESIS</subject><ispartof>J. Am. Chem. Soc.; (United States), 1988-08, Vol.110 (17), p.5791-5799</ispartof><rights>1990 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a423t-fcf1dc2a5ba7b67a61b7ed93cad4804af7016367f2cb173cb79dd45d43e7b1053</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja00225a034$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja00225a034$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,885,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=6762864$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/6084347$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Orr, Gary R</creatorcontrib><creatorcontrib>Danz, Deborah W</creatorcontrib><creatorcontrib>Pontoni, Gabriele</creatorcontrib><creatorcontrib>Prabhakaran, P. C</creatorcontrib><creatorcontrib>Gould, Steven J</creatorcontrib><creatorcontrib>Coward, James K</creatorcontrib><creatorcontrib>Rensselaer Polytechnic Institute, Troy, NY (USA)</creatorcontrib><title>Synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and spermidines. Elucidation of the stereochemical course of putrescine aminopropyltransferase (spermidine synthase)</title><title>J. Am. Chem. Soc.; (United States)</title><addtitle>J. Am. Chem. Soc</addtitle><description>The stereochemical course of enzyme-catalyzed aminopropyl transfer has been investigated. The stereospecific synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and several chirally deuteriated spermidine (-)-camphanamide derivatives has allowed the elucidation of aminopropyltransferase stereochemistry by using /sup 1/H NMR techniques. Putrescine aminopropyltransferase (spermidine synthase) isolated from Eschierchia coli catalyzed the synthesis of chirally deuteriated spermidines from 1,4-diaminobutane (putrescine) and chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines. Derivatization of the biosynthetic spermidines to 1,8-bis(Boc)spermidine (-)-camphanamides and comparison of their /sup 1/H NMR spectra with those of the synthetic standards permits determination of the absolute configuration of the biosynthetic products. The results show that the reaction catalyzed by E. coli spermidine synthase proceeds with inversion of configuration at the methylene carbon undergoing nucleophilic attack by putrescine. These data support a single-displacement mechanism proceeding via a ternary complex of enzyme and both substrates. 42 references, 5 figures.</description><subject>400201 - Chemical & Physicochemical Properties</subject><subject>400202 - Isotope Effects, Isotope Exchange, & Isotope Separation</subject><subject>Aliphatic compounds</subject><subject>ALKANES</subject><subject>AMINES</subject><subject>Chemistry</subject><subject>DATA</subject><subject>DEUTERIUM</subject><subject>Exact sciences and technology</subject><subject>EXPERIMENTAL DATA</subject><subject>HYDROCARBONS</subject><subject>HYDROGEN ISOTOPES</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>ISOTOPES</subject><subject>LABELLED COMPOUNDS</subject><subject>LIGHT NUCLEI</subject><subject>NUCLEI</subject><subject>NUMERICAL DATA</subject><subject>ODD-ODD NUCLEI</subject><subject>Organic chemistry</subject><subject>ORGANIC COMPOUNDS</subject><subject>Preparations and properties</subject><subject>SPERMIDINE</subject><subject>STABLE ISOTOPES</subject><subject>SYNTHESIS</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1988</creationdate><recordtype>article</recordtype><recordid>eNptkd2K1TAUhYsoeBy98gWCCM4gHfPTJp1LOYyOOOjAGfEy7OaH5tiTlCQF-3Y-mimV0Quvws769srO2lX1kuBLgil5dwSMKW0Bs-ZRtSMtxXVLKH9c7XARatFx9rR6ltKxlA3tyK76dVh8HkxyCQWL1OAijOOCtJmziQ6y0ej8UIM2PqRlrA_1yeRhGdM82uBduJhimJYRTs6bhMBrlCYTT06v9SW6HmflNGQX_GpfHkKp-JqgBnNyCkakwhyTWcVpztEkVRrRahc25xzBJ2siFOj8rzdK69jl8uJ59cTCmMyLP-dZ9e3D9f3-pr79-vHT_v1tDQ1lubbKEq0otD2IngvgpBdGXzEFuulwA1ZgwhkXlqqeCKZ6caV10-qGGdET3LKz6tXmG1J2ssyZjRpU8N6oLDnuGtaIAr3dIBVDStFYOUV3grhIguW6IfnPhgr9eqMnSCULW76qXHpo4YLTjq9YvWGuZPfzQYb4oyBMtPL-7iC7Lzd7ccc_y--Ff7PxoJI8lnx9yeW_A_wGmkeyyQ</recordid><startdate>198808</startdate><enddate>198808</enddate><creator>Orr, Gary R</creator><creator>Danz, Deborah W</creator><creator>Pontoni, Gabriele</creator><creator>Prabhakaran, P. C</creator><creator>Gould, Steven J</creator><creator>Coward, James K</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>198808</creationdate><title>Synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and spermidines. Elucidation of the stereochemical course of putrescine aminopropyltransferase (spermidine synthase)</title><author>Orr, Gary R ; Danz, Deborah W ; Pontoni, Gabriele ; Prabhakaran, P. C ; Gould, Steven J ; Coward, James K</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a423t-fcf1dc2a5ba7b67a61b7ed93cad4804af7016367f2cb173cb79dd45d43e7b1053</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1988</creationdate><topic>400201 - Chemical & Physicochemical Properties</topic><topic>400202 - Isotope Effects, Isotope Exchange, & Isotope Separation</topic><topic>Aliphatic compounds</topic><topic>ALKANES</topic><topic>AMINES</topic><topic>Chemistry</topic><topic>DATA</topic><topic>DEUTERIUM</topic><topic>Exact sciences and technology</topic><topic>EXPERIMENTAL DATA</topic><topic>HYDROCARBONS</topic><topic>HYDROGEN ISOTOPES</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>ISOTOPES</topic><topic>LABELLED COMPOUNDS</topic><topic>LIGHT NUCLEI</topic><topic>NUCLEI</topic><topic>NUMERICAL DATA</topic><topic>ODD-ODD NUCLEI</topic><topic>Organic chemistry</topic><topic>ORGANIC COMPOUNDS</topic><topic>Preparations and properties</topic><topic>SPERMIDINE</topic><topic>STABLE ISOTOPES</topic><topic>SYNTHESIS</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Orr, Gary R</creatorcontrib><creatorcontrib>Danz, Deborah W</creatorcontrib><creatorcontrib>Pontoni, Gabriele</creatorcontrib><creatorcontrib>Prabhakaran, P. C</creatorcontrib><creatorcontrib>Gould, Steven J</creatorcontrib><creatorcontrib>Coward, James K</creatorcontrib><creatorcontrib>Rensselaer Polytechnic Institute, Troy, NY (USA)</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Am. Chem. Soc.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Orr, Gary R</au><au>Danz, Deborah W</au><au>Pontoni, Gabriele</au><au>Prabhakaran, P. C</au><au>Gould, Steven J</au><au>Coward, James K</au><aucorp>Rensselaer Polytechnic Institute, Troy, NY (USA)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and spermidines. Elucidation of the stereochemical course of putrescine aminopropyltransferase (spermidine synthase)</atitle><jtitle>J. Am. Chem. Soc.; (United States)</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>1988-08</date><risdate>1988</risdate><volume>110</volume><issue>17</issue><spage>5791</spage><epage>5799</epage><pages>5791-5799</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>The stereochemical course of enzyme-catalyzed aminopropyl transfer has been investigated. The stereospecific synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and several chirally deuteriated spermidine (-)-camphanamide derivatives has allowed the elucidation of aminopropyltransferase stereochemistry by using /sup 1/H NMR techniques. Putrescine aminopropyltransferase (spermidine synthase) isolated from Eschierchia coli catalyzed the synthesis of chirally deuteriated spermidines from 1,4-diaminobutane (putrescine) and chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines. Derivatization of the biosynthetic spermidines to 1,8-bis(Boc)spermidine (-)-camphanamides and comparison of their /sup 1/H NMR spectra with those of the synthetic standards permits determination of the absolute configuration of the biosynthetic products. The results show that the reaction catalyzed by E. coli spermidine synthase proceeds with inversion of configuration at the methylene carbon undergoing nucleophilic attack by putrescine. These data support a single-displacement mechanism proceeding via a ternary complex of enzyme and both substrates. 42 references, 5 figures.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/ja00225a034</doi><tpages>9</tpages></addata></record> |
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| ispartof | J. Am. Chem. Soc.; (United States), 1988-08, Vol.110 (17), p.5791-5799 |
| issn | 0002-7863 1520-5126 |
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| source | ACS Publications |
| subjects | 400201 - Chemical & Physicochemical Properties 400202 - Isotope Effects, Isotope Exchange, & Isotope Separation Aliphatic compounds ALKANES AMINES Chemistry DATA DEUTERIUM Exact sciences and technology EXPERIMENTAL DATA HYDROCARBONS HYDROGEN ISOTOPES INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ISOTOPES LABELLED COMPOUNDS LIGHT NUCLEI NUCLEI NUMERICAL DATA ODD-ODD NUCLEI Organic chemistry ORGANIC COMPOUNDS Preparations and properties SPERMIDINE STABLE ISOTOPES SYNTHESIS |
| title | Synthesis of chirally deuteriated (S-adenosyl-S-methylsulfonio)propylamines and spermidines. Elucidation of the stereochemical course of putrescine aminopropyltransferase (spermidine synthase) |
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