Werner Complexes with ω-Dimethylaminoalkyl Substituted Ethylenediamine Ligands: Bifunctional Hydrogen-Bond-Donor Catalysts for Highly Enantioselective Michael Additions
The racemic carbonate complex [Co(en)2O2CO]+ Cl− (en=1,2‐ethylenediamine) and (S)‐[H3NCH((CH2)nNHMe2)CH2NH3]3+ 3 Cl− (n=1–4) react (water, charcoal, 100 °C) to give [Co(en)2((S)‐H2NCH((CH2)nNHMe2)CH2NH2)]4+ 4 Cl− (3 a–d H4+ 4 Cl−) as a mixture of Λ/Δ diastereomers that separate on chiral‐phase Sepha...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2016-03, Vol.55 (13), p.4356-4360 |
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| creator | Ghosh, Subrata K. Ganzmann, Carola Bhuvanesh, Nattamai Gladysz, John A. |
| description | The racemic carbonate complex [Co(en)2O2CO]+ Cl− (en=1,2‐ethylenediamine) and (S)‐[H3NCH((CH2)nNHMe2)CH2NH3]3+ 3 Cl− (n=1–4) react (water, charcoal, 100 °C) to give [Co(en)2((S)‐H2NCH((CH2)nNHMe2)CH2NH2)]4+ 4 Cl− (3 a–d H4+ 4 Cl−) as a mixture of Λ/Δ diastereomers that separate on chiral‐phase Sephadex columns. These are treated with NaOH/Na+ BArf− (BArf=B(3,5‐C6H3(CF3)2)4) to give lipophilic Λ‐ and Δ‐3 a–d3+ 3 BArf−, which are screened as catalysts (10 mol %) for additions of dialkyl malonates to nitroalkenes. Optimal results are obtained with Λ‐3 c3+ 3 BArf− (CH2Cl2, −35 °C; 98–82 % yields and 99–93 % ee for six β‐arylnitroethenes). The monofunctional catalysts Λ‐ and Δ‐[Co(en)3]3+ 3 BArf− give enantioselectivities of |
| doi_str_mv | 10.1002/anie.201511314 |
| format | Article |
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Two are better than one: Unlike the catalyst Λ‐[Co(en)3]3+ 3 BArf−, the bifunctional tertiary‐amine‐containing analogue Λ‐3 c3+ 3 BArf− effects highly enantioselective additions of alkyl malonates to β‐aryl‐ and β‐alkylnitroethenes. The efficacy diminishes as the (CH2)3 tether is shortened or lengthened.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201511314</identifier><identifier>PMID: 26918320</identifier><language>eng</language><publisher>Germany: Blackwell Publishing Ltd</publisher><subject>Catalysis ; Catalysts ; Charcoal ; cobalt complexes ; Crystal structure ; Dichloromethane ; Enantiomers ; enantioselective catalysis ; Ethylenediamine ; hydrogen bonding ; Lipophilic ; Michael additions ; nitroalkenes ; Sodium hydroxide</subject><ispartof>Angewandte Chemie International Edition, 2016-03, Vol.55 (13), p.4356-4360</ispartof><rights>2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3964-6925cae670c82cbc49e5609dddf93b52190f8ad706b7eecde3ae42c8478b50a3</citedby><cites>FETCH-LOGICAL-c3964-6925cae670c82cbc49e5609dddf93b52190f8ad706b7eecde3ae42c8478b50a3</cites><orcidid>0000-0002-7012-4872</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.201511314$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201511314$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27903,27904,45553,45554</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/26918320$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Ghosh, Subrata K.</creatorcontrib><creatorcontrib>Ganzmann, Carola</creatorcontrib><creatorcontrib>Bhuvanesh, Nattamai</creatorcontrib><creatorcontrib>Gladysz, John A.</creatorcontrib><title>Werner Complexes with ω-Dimethylaminoalkyl Substituted Ethylenediamine Ligands: Bifunctional Hydrogen-Bond-Donor Catalysts for Highly Enantioselective Michael Additions</title><title>Angewandte Chemie International Edition</title><addtitle>Angew. Chem. Int. Ed</addtitle><description>The racemic carbonate complex [Co(en)2O2CO]+ Cl− (en=1,2‐ethylenediamine) and (S)‐[H3NCH((CH2)nNHMe2)CH2NH3]3+ 3 Cl− (n=1–4) react (water, charcoal, 100 °C) to give [Co(en)2((S)‐H2NCH((CH2)nNHMe2)CH2NH2)]4+ 4 Cl− (3 a–d H4+ 4 Cl−) as a mixture of Λ/Δ diastereomers that separate on chiral‐phase Sephadex columns. These are treated with NaOH/Na+ BArf− (BArf=B(3,5‐C6H3(CF3)2)4) to give lipophilic Λ‐ and Δ‐3 a–d3+ 3 BArf−, which are screened as catalysts (10 mol %) for additions of dialkyl malonates to nitroalkenes. Optimal results are obtained with Λ‐3 c3+ 3 BArf− (CH2Cl2, −35 °C; 98–82 % yields and 99–93 % ee for six β‐arylnitroethenes). The monofunctional catalysts Λ‐ and Δ‐[Co(en)3]3+ 3 BArf− give enantioselectivities of <10 % ee with equal loadings of Et3N. The crystal structure of Δ‐3 a H4+ 4 Cl− provides a starting point for speculation regarding transition‐state assemblies.
Two are better than one: Unlike the catalyst Λ‐[Co(en)3]3+ 3 BArf−, the bifunctional tertiary‐amine‐containing analogue Λ‐3 c3+ 3 BArf− effects highly enantioselective additions of alkyl malonates to β‐aryl‐ and β‐alkylnitroethenes. The efficacy diminishes as the (CH2)3 tether is shortened or lengthened.</description><subject>Catalysis</subject><subject>Catalysts</subject><subject>Charcoal</subject><subject>cobalt complexes</subject><subject>Crystal structure</subject><subject>Dichloromethane</subject><subject>Enantiomers</subject><subject>enantioselective catalysis</subject><subject>Ethylenediamine</subject><subject>hydrogen bonding</subject><subject>Lipophilic</subject><subject>Michael additions</subject><subject>nitroalkenes</subject><subject>Sodium hydroxide</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqFkUFv0zAYhiMEYmNw5YgsceGSYsdJnHDr2rJOKuPQST1ajv2l9ebYJXbY8hP4Kfwa_hKuOirEhZNt-Xkfy9-bJG8JnhCMs4_CaphkmBSEUJI_S85JkZGUMkafx31Oacqqgpwlr7y_i3xV4fJlcpaVNalohs-TnxvoLfRo5rq9gUfw6EGHHfr1I53rDsJuNKLT1glzPxq0HhofdBgCKLQ43IEFpQ8AoJXeCqv8J3Sp28HKoJ0VBi1H1bst2PTSWZXOnXXxKRGEGX3wqI2npd7uzIgWVtiY8WAgZr8D-qLlToBBU6X0QeZfJy9aYTy8eVovktvPi9vZMl19vbqeTVeppHWZp2WdFVJAybCsMtnIvIaixLVSqq1pE4dT47YSiuGyYQBSARWQZ7LKWdUUWNCL5MNRu-_dtwF84J32EowRFtzgOWGsoHF2eRXR9_-gd27o47c9z3DBcFbkNY7U5EjJ3nnfQ8v3ve5EP3KC-aFDfuiQnzqMgXdP2qHpQJ3wP6VFoD4CD9rA-B8dn95cL_6Wp8es9gEeT1nR3_OSUVbwzc0Vn7NqvVnPVhzT3-OAvFc</recordid><startdate>20160318</startdate><enddate>20160318</enddate><creator>Ghosh, Subrata K.</creator><creator>Ganzmann, Carola</creator><creator>Bhuvanesh, Nattamai</creator><creator>Gladysz, John A.</creator><general>Blackwell Publishing Ltd</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-7012-4872</orcidid></search><sort><creationdate>20160318</creationdate><title>Werner Complexes with ω-Dimethylaminoalkyl Substituted Ethylenediamine Ligands: Bifunctional Hydrogen-Bond-Donor Catalysts for Highly Enantioselective Michael Additions</title><author>Ghosh, Subrata K. ; Ganzmann, Carola ; Bhuvanesh, Nattamai ; Gladysz, John A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3964-6925cae670c82cbc49e5609dddf93b52190f8ad706b7eecde3ae42c8478b50a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Catalysis</topic><topic>Catalysts</topic><topic>Charcoal</topic><topic>cobalt complexes</topic><topic>Crystal structure</topic><topic>Dichloromethane</topic><topic>Enantiomers</topic><topic>enantioselective catalysis</topic><topic>Ethylenediamine</topic><topic>hydrogen bonding</topic><topic>Lipophilic</topic><topic>Michael additions</topic><topic>nitroalkenes</topic><topic>Sodium hydroxide</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ghosh, Subrata K.</creatorcontrib><creatorcontrib>Ganzmann, Carola</creatorcontrib><creatorcontrib>Bhuvanesh, Nattamai</creatorcontrib><creatorcontrib>Gladysz, John A.</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ghosh, Subrata K.</au><au>Ganzmann, Carola</au><au>Bhuvanesh, Nattamai</au><au>Gladysz, John A.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Werner Complexes with ω-Dimethylaminoalkyl Substituted Ethylenediamine Ligands: Bifunctional Hydrogen-Bond-Donor Catalysts for Highly Enantioselective Michael Additions</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2016-03-18</date><risdate>2016</risdate><volume>55</volume><issue>13</issue><spage>4356</spage><epage>4360</epage><pages>4356-4360</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>The racemic carbonate complex [Co(en)2O2CO]+ Cl− (en=1,2‐ethylenediamine) and (S)‐[H3NCH((CH2)nNHMe2)CH2NH3]3+ 3 Cl− (n=1–4) react (water, charcoal, 100 °C) to give [Co(en)2((S)‐H2NCH((CH2)nNHMe2)CH2NH2)]4+ 4 Cl− (3 a–d H4+ 4 Cl−) as a mixture of Λ/Δ diastereomers that separate on chiral‐phase Sephadex columns. These are treated with NaOH/Na+ BArf− (BArf=B(3,5‐C6H3(CF3)2)4) to give lipophilic Λ‐ and Δ‐3 a–d3+ 3 BArf−, which are screened as catalysts (10 mol %) for additions of dialkyl malonates to nitroalkenes. Optimal results are obtained with Λ‐3 c3+ 3 BArf− (CH2Cl2, −35 °C; 98–82 % yields and 99–93 % ee for six β‐arylnitroethenes). The monofunctional catalysts Λ‐ and Δ‐[Co(en)3]3+ 3 BArf− give enantioselectivities of <10 % ee with equal loadings of Et3N. The crystal structure of Δ‐3 a H4+ 4 Cl− provides a starting point for speculation regarding transition‐state assemblies.
Two are better than one: Unlike the catalyst Λ‐[Co(en)3]3+ 3 BArf−, the bifunctional tertiary‐amine‐containing analogue Λ‐3 c3+ 3 BArf− effects highly enantioselective additions of alkyl malonates to β‐aryl‐ and β‐alkylnitroethenes. The efficacy diminishes as the (CH2)3 tether is shortened or lengthened.</abstract><cop>Germany</cop><pub>Blackwell Publishing Ltd</pub><pmid>26918320</pmid><doi>10.1002/anie.201511314</doi><tpages>5</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-7012-4872</orcidid></addata></record> |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Catalysis Catalysts Charcoal cobalt complexes Crystal structure Dichloromethane Enantiomers enantioselective catalysis Ethylenediamine hydrogen bonding Lipophilic Michael additions nitroalkenes Sodium hydroxide |
| title | Werner Complexes with ω-Dimethylaminoalkyl Substituted Ethylenediamine Ligands: Bifunctional Hydrogen-Bond-Donor Catalysts for Highly Enantioselective Michael Additions |
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