Amine(imine) diphosphine Iron Catalysts for Asymmetric Transfer Hydrogenation of Ketones and Imines
A rational approach is needed to design hydrogénation catalysts that make use of Earth-abundant elements to replace the rare elements such as ruthenium, rhodium, and palladium that are traditionally used. Here, we validate a prior mechanistic hypothesis that partially saturated amine(imine) diphosph...
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| Veröffentlicht in: | Science (American Association for the Advancement of Science) 2013-11, Vol.342 (6162), p.1080-1083 |
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| container_title | Science (American Association for the Advancement of Science) |
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| creator | Zuo, Weiwei Lough, Alan J. Li, Young Feng Morris, Robert H. |
| description | A rational approach is needed to design hydrogénation catalysts that make use of Earth-abundant elements to replace the rare elements such as ruthenium, rhodium, and palladium that are traditionally used. Here, we validate a prior mechanistic hypothesis that partially saturated amine(imine) diphosphine ligands (P-NH-N-P) activate iron to catalyze the asymmetric reduction of the polar bonds of ketones and imines to valuable enantiopure alcohols and amines, with isopropanol as the hydrogen donor, at turnover frequencies as high as 200 per second at 28°C. We present a direct synthetic approach to enantiopure ligands of this type that takes advantage of the iron(ll) ion as a template. The catalytic mechanism is elucidated by the spectroscopic detection of iron hydride and amide intermediates. |
| doi_str_mv | 10.1126/science.1244466 |
| format | Article |
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Here, we validate a prior mechanistic hypothesis that partially saturated amine(imine) diphosphine ligands (P-NH-N-P) activate iron to catalyze the asymmetric reduction of the polar bonds of ketones and imines to valuable enantiopure alcohols and amines, with isopropanol as the hydrogen donor, at turnover frequencies as high as 200 per second at 28°C. We present a direct synthetic approach to enantiopure ligands of this type that takes advantage of the iron(ll) ion as a template. 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Nomenclature, chemical documentation, computer chemistry ; Trace elements</subject><ispartof>Science (American Association for the Advancement of Science), 2013-11, Vol.342 (6162), p.1080-1083</ispartof><rights>Copyright © 2013 American Association for the Advancement of Science</rights><rights>2015 INIST-CNRS</rights><rights>Copyright © 2013, American Association for the Advancement of Science</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c513t-3e69bdc399c78f0f95f31fa59d203c1bce000375e3f1688fe964ecd8dfaea6a53</citedby><cites>FETCH-LOGICAL-c513t-3e69bdc399c78f0f95f31fa59d203c1bce000375e3f1688fe964ecd8dfaea6a53</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.jstor.org/stable/pdf/42913775$$EPDF$$P50$$Gjstor$$H</linktopdf><linktohtml>$$Uhttps://www.jstor.org/stable/42913775$$EHTML$$P50$$Gjstor$$H</linktohtml><link.rule.ids>314,776,780,799,2871,2872,27901,27902,57992,58225</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=28073682$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/24288329$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Zuo, Weiwei</creatorcontrib><creatorcontrib>Lough, Alan J.</creatorcontrib><creatorcontrib>Li, Young Feng</creatorcontrib><creatorcontrib>Morris, Robert H.</creatorcontrib><title>Amine(imine) diphosphine Iron Catalysts for Asymmetric Transfer Hydrogenation of Ketones and Imines</title><title>Science (American Association for the Advancement of Science)</title><addtitle>Science</addtitle><description>A rational approach is needed to design hydrogénation catalysts that make use of Earth-abundant elements to replace the rare elements such as ruthenium, rhodium, and palladium that are traditionally used. 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The catalytic mechanism is elucidated by the spectroscopic detection of iron hydride and amide intermediates.</description><subject>Alcohols</subject><subject>Amines</subject><subject>Asymmetry</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Chemistry</subject><subject>Cobalt</subject><subject>Diamines</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Hydrides</subject><subject>Hydrogen</subject><subject>Hydrogenation</subject><subject>Imines</subject><subject>Iron</subject><subject>Ketones</subject><subject>Ligands</subject><subject>Palladium</subject><subject>Studies</subject><subject>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</subject><subject>Trace elements</subject><issn>0036-8075</issn><issn>1095-9203</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><recordid>eNqFkc9rFDEYhoModq2ePSkBEeph2vyYZCbHZVG7WPBSz0M288VmmUnWfLOH_e-bcccKXrwkhO_JC-_3EPKWs2vOhb5BFyA6uOairmutn5EVZ0ZVRjD5nKwYk7pqWaMuyCvEPWNlZuRLciFq0bZSmBVx6zFEuArz-Yn24fCQ8PBQHnSbU6QbO9nhhBNSnzJd42kcYcrB0ftsI3rI9PbU5_QTop1C4ZOn32BKEZDa2NPtHIuvyQtvB4Q3y31Jfnz5fL-5re6-f91u1neVU1xOlQRtdr2Txrim9cwb5SX3Vpm-tHF856AUkI0C6bluWw9G1-D6tvcWrLZKXpKrc-4hp19HwKkbAzoYBhshHbHjShltJG_E_9Fai0aXNc2pH_5B9-mYYynym2pFU0tWqJsz5XJCzOC7Qw6jzaeOs25W1S2qukVV-fF-yT3uRuif-D9uCvBxASw6O_iycRfwL1fESt3OXd6duT1OKT_Na2G4bBolHwEWoqcQ</recordid><startdate>20131129</startdate><enddate>20131129</enddate><creator>Zuo, Weiwei</creator><creator>Lough, Alan J.</creator><creator>Li, Young Feng</creator><creator>Morris, Robert H.</creator><general>American Association for the Advancement of Science</general><general>The American Association for the Advancement of Science</general><scope>IQODW</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QF</scope><scope>7QG</scope><scope>7QL</scope><scope>7QP</scope><scope>7QQ</scope><scope>7QR</scope><scope>7SC</scope><scope>7SE</scope><scope>7SN</scope><scope>7SP</scope><scope>7SR</scope><scope>7SS</scope><scope>7T7</scope><scope>7TA</scope><scope>7TB</scope><scope>7TK</scope><scope>7TM</scope><scope>7U5</scope><scope>7U9</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>F28</scope><scope>FR3</scope><scope>H8D</scope><scope>H8G</scope><scope>H94</scope><scope>JG9</scope><scope>JQ2</scope><scope>K9.</scope><scope>KR7</scope><scope>L7M</scope><scope>L~C</scope><scope>L~D</scope><scope>M7N</scope><scope>P64</scope><scope>RC3</scope><scope>7X8</scope></search><sort><creationdate>20131129</creationdate><title>Amine(imine) diphosphine Iron Catalysts for Asymmetric Transfer Hydrogenation of Ketones and Imines</title><author>Zuo, Weiwei ; Lough, Alan J. ; Li, Young Feng ; Morris, Robert H.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c513t-3e69bdc399c78f0f95f31fa59d203c1bce000375e3f1688fe964ecd8dfaea6a53</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><topic>Alcohols</topic><topic>Amines</topic><topic>Asymmetry</topic><topic>Catalysis</topic><topic>Catalysts</topic><topic>Chemistry</topic><topic>Cobalt</topic><topic>Diamines</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>Hydrides</topic><topic>Hydrogen</topic><topic>Hydrogenation</topic><topic>Imines</topic><topic>Iron</topic><topic>Ketones</topic><topic>Ligands</topic><topic>Palladium</topic><topic>Studies</topic><topic>Theory of reactions, general kinetics. 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Nomenclature, chemical documentation, computer chemistry</topic><topic>Trace elements</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zuo, Weiwei</creatorcontrib><creatorcontrib>Lough, Alan J.</creatorcontrib><creatorcontrib>Li, Young Feng</creatorcontrib><creatorcontrib>Morris, Robert H.</creatorcontrib><collection>Pascal-Francis</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Aluminium Industry Abstracts</collection><collection>Animal Behavior Abstracts</collection><collection>Bacteriology Abstracts (Microbiology B)</collection><collection>Calcium & Calcified Tissue Abstracts</collection><collection>Ceramic Abstracts</collection><collection>Chemoreception Abstracts</collection><collection>Computer and Information Systems Abstracts</collection><collection>Corrosion Abstracts</collection><collection>Ecology Abstracts</collection><collection>Electronics & Communications Abstracts</collection><collection>Engineered Materials Abstracts</collection><collection>Entomology Abstracts (Full archive)</collection><collection>Industrial and Applied Microbiology Abstracts (Microbiology A)</collection><collection>Materials Business File</collection><collection>Mechanical & Transportation Engineering Abstracts</collection><collection>Neurosciences Abstracts</collection><collection>Nucleic Acids Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Virology and AIDS Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>ANTE: Abstracts in New Technology & Engineering</collection><collection>Engineering Research Database</collection><collection>Aerospace Database</collection><collection>Copper Technical Reference Library</collection><collection>AIDS and Cancer Research Abstracts</collection><collection>Materials Research Database</collection><collection>ProQuest Computer Science Collection</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>Civil Engineering Abstracts</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>Computer and Information Systems Abstracts Academic</collection><collection>Computer and Information Systems Abstracts Professional</collection><collection>Algology Mycology and Protozoology Abstracts (Microbiology C)</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>Genetics Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Science (American Association for the Advancement of Science)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zuo, Weiwei</au><au>Lough, Alan J.</au><au>Li, Young Feng</au><au>Morris, Robert H.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Amine(imine) diphosphine Iron Catalysts for Asymmetric Transfer Hydrogenation of Ketones and Imines</atitle><jtitle>Science (American Association for the Advancement of Science)</jtitle><addtitle>Science</addtitle><date>2013-11-29</date><risdate>2013</risdate><volume>342</volume><issue>6162</issue><spage>1080</spage><epage>1083</epage><pages>1080-1083</pages><issn>0036-8075</issn><eissn>1095-9203</eissn><coden>SCIEAS</coden><abstract>A rational approach is needed to design hydrogénation catalysts that make use of Earth-abundant elements to replace the rare elements such as ruthenium, rhodium, and palladium that are traditionally used. Here, we validate a prior mechanistic hypothesis that partially saturated amine(imine) diphosphine ligands (P-NH-N-P) activate iron to catalyze the asymmetric reduction of the polar bonds of ketones and imines to valuable enantiopure alcohols and amines, with isopropanol as the hydrogen donor, at turnover frequencies as high as 200 per second at 28°C. We present a direct synthetic approach to enantiopure ligands of this type that takes advantage of the iron(ll) ion as a template. The catalytic mechanism is elucidated by the spectroscopic detection of iron hydride and amide intermediates.</abstract><cop>Washington, DC</cop><pub>American Association for the Advancement of Science</pub><pmid>24288329</pmid><doi>10.1126/science.1244466</doi><tpages>4</tpages></addata></record> |
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| source | Jstor Complete Legacy; Science Magazine |
| subjects | Alcohols Amines Asymmetry Catalysis Catalysts Chemistry Cobalt Diamines Exact sciences and technology General and physical chemistry Hydrides Hydrogen Hydrogenation Imines Iron Ketones Ligands Palladium Studies Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry Trace elements |
| title | Amine(imine) diphosphine Iron Catalysts for Asymmetric Transfer Hydrogenation of Ketones and Imines |
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