Copper Complexes with Protein‐Based N‐Donor Ligands as cis‐Selective Nascent Cyclopropanases
In this study, we aimed to develop protein‐based metal ligands to catalyze cis‐selective cyclopropanation using the TM1459 cupin protein superfamily. Copper complexes with TM1459 mutants containing the 3‐His metal‐binding site exhibited excellent diastereoselectivity in cyclopropanation reactions wi...
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| Veröffentlicht in: | Chemistry : a European journal 2024-12, Vol.30 (70), p.e202402803-n/a |
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| creator | Fujieda, Nobutaka Matsuo, Atsuki Itoh, Shinobu |
| description | In this study, we aimed to develop protein‐based metal ligands to catalyze cis‐selective cyclopropanation using the TM1459 cupin protein superfamily. Copper complexes with TM1459 mutants containing the 3‐His metal‐binding site exhibited excellent diastereoselectivity in cyclopropanation reactions with styrene and ethyl diazoacetate. Further mutations in the secondary coordination sphere increased the cis‐preference with t‐butyl diazoacetate as the substrate with up to 80 : 20 (cis:trans ratio) and high enantioselectivity (90 % ee).
Stepwise repurposing of the first and second coordination spheres in cupin proteins yielded novel copper cupin complexes that could catalyze diastereo‐ and enantioselective cyclopropanation reactions via copper carbene species using ethyl diazoacetate. Even when employing t‐butyl diazoacetate which is too bulky to produce the cis‐cyclopropane, these nascent cyclopropanases exhibited thermodynamically unfavorable cis‐preference. |
| doi_str_mv | 10.1002/chem.202402803 |
| format | Article |
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Stepwise repurposing of the first and second coordination spheres in cupin proteins yielded novel copper cupin complexes that could catalyze diastereo‐ and enantioselective cyclopropanation reactions via copper carbene species using ethyl diazoacetate. Even when employing t‐butyl diazoacetate which is too bulky to produce the cis‐cyclopropane, these nascent cyclopropanases exhibited thermodynamically unfavorable cis‐preference.</description><identifier>ISSN: 0947-6539</identifier><identifier>ISSN: 1521-3765</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.202402803</identifier><identifier>PMID: 39258820</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Artificial metalloenzymes ; Binding Sites ; Catalysis ; Coordination Complexes - chemistry ; Copper ; Copper - chemistry ; Copper compounds ; Cupin ; Cyclopropanation ; Cyclopropanes - chemistry ; Enantiomers ; Ligands ; Metallocarbene ; Mononuclear copper enzyme ; Proteins ; Stereoisomerism ; Stereoselectivity ; Styrene ; Styrene - chemistry</subject><ispartof>Chemistry : a European journal, 2024-12, Vol.30 (70), p.e202402803-n/a</ispartof><rights>2024 Wiley-VCH GmbH</rights><rights>2024 Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c2583-bd077facca7063024fe069d77ab395ca6e57af8637367c0bfa71e8f20298a30f3</cites><orcidid>0000-0003-1045-6063 ; 0000-0002-3711-2378</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%2Fchem.202402803$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.202402803$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/39258820$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Fujieda, Nobutaka</creatorcontrib><creatorcontrib>Matsuo, Atsuki</creatorcontrib><creatorcontrib>Itoh, Shinobu</creatorcontrib><title>Copper Complexes with Protein‐Based N‐Donor Ligands as cis‐Selective Nascent Cyclopropanases</title><title>Chemistry : a European journal</title><addtitle>Chemistry</addtitle><description>In this study, we aimed to develop protein‐based metal ligands to catalyze cis‐selective cyclopropanation using the TM1459 cupin protein superfamily. Copper complexes with TM1459 mutants containing the 3‐His metal‐binding site exhibited excellent diastereoselectivity in cyclopropanation reactions with styrene and ethyl diazoacetate. Further mutations in the secondary coordination sphere increased the cis‐preference with t‐butyl diazoacetate as the substrate with up to 80 : 20 (cis:trans ratio) and high enantioselectivity (90 % ee).
Stepwise repurposing of the first and second coordination spheres in cupin proteins yielded novel copper cupin complexes that could catalyze diastereo‐ and enantioselective cyclopropanation reactions via copper carbene species using ethyl diazoacetate. Even when employing t‐butyl diazoacetate which is too bulky to produce the cis‐cyclopropane, these nascent cyclopropanases exhibited thermodynamically unfavorable cis‐preference.</description><subject>Artificial metalloenzymes</subject><subject>Binding Sites</subject><subject>Catalysis</subject><subject>Coordination Complexes - chemistry</subject><subject>Copper</subject><subject>Copper - chemistry</subject><subject>Copper compounds</subject><subject>Cupin</subject><subject>Cyclopropanation</subject><subject>Cyclopropanes - chemistry</subject><subject>Enantiomers</subject><subject>Ligands</subject><subject>Metallocarbene</subject><subject>Mononuclear copper enzyme</subject><subject>Proteins</subject><subject>Stereoisomerism</subject><subject>Stereoselectivity</subject><subject>Styrene</subject><subject>Styrene - chemistry</subject><issn>0947-6539</issn><issn>1521-3765</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqFkLlOxDAURS0EgmFpKZElGpoML3FixyWEYZGGRQLqyHFeICiJg50BpuMT-Ea-BKNhkWiobFnnXd93CNkOYRwCRPv6HttxBFEMUQpsiYzCJAoDJniyTEYgYxHwhMk1su7cAwBIztgqWWMyStI0ghEpMtP3aGlm2r7BF3T0uR7u6ZU1A9bd--vboXJY0gt_OzKdsXRa36mudFQ5qmvnn6-xQT3UT0gvlNPYDTSb68b01vSq88Nuk6xUqnG49XVukNvjyU12GkwvT86yg2mgfRkWFCUIUSmtlQDO_EYVApelEKpgMtGKYyJUlXImGBcaikqJENPK7y5TxaBiG2Rvkeu_fpyhG_K29oWaRnVoZi5noXeUhnHMPbr7B30wM9v5dp6KWQqS8dhT4wWlrXHOYpX3tm6Vnech5J_280_7-Y99P7DzFTsrWix_8G_dHpAL4LlucP5PXJ6dTs5_wz8Aq--Trw</recordid><startdate>20241213</startdate><enddate>20241213</enddate><creator>Fujieda, Nobutaka</creator><creator>Matsuo, Atsuki</creator><creator>Itoh, Shinobu</creator><general>Wiley Subscription Services, Inc</general><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>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-1045-6063</orcidid><orcidid>https://orcid.org/0000-0002-3711-2378</orcidid></search><sort><creationdate>20241213</creationdate><title>Copper Complexes with Protein‐Based N‐Donor Ligands as cis‐Selective Nascent Cyclopropanases</title><author>Fujieda, Nobutaka ; Matsuo, Atsuki ; Itoh, Shinobu</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2583-bd077facca7063024fe069d77ab395ca6e57af8637367c0bfa71e8f20298a30f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Artificial metalloenzymes</topic><topic>Binding Sites</topic><topic>Catalysis</topic><topic>Coordination Complexes - chemistry</topic><topic>Copper</topic><topic>Copper - chemistry</topic><topic>Copper compounds</topic><topic>Cupin</topic><topic>Cyclopropanation</topic><topic>Cyclopropanes - chemistry</topic><topic>Enantiomers</topic><topic>Ligands</topic><topic>Metallocarbene</topic><topic>Mononuclear copper enzyme</topic><topic>Proteins</topic><topic>Stereoisomerism</topic><topic>Stereoselectivity</topic><topic>Styrene</topic><topic>Styrene - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Fujieda, Nobutaka</creatorcontrib><creatorcontrib>Matsuo, Atsuki</creatorcontrib><creatorcontrib>Itoh, Shinobu</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Fujieda, Nobutaka</au><au>Matsuo, Atsuki</au><au>Itoh, Shinobu</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Copper Complexes with Protein‐Based N‐Donor Ligands as cis‐Selective Nascent Cyclopropanases</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry</addtitle><date>2024-12-13</date><risdate>2024</risdate><volume>30</volume><issue>70</issue><spage>e202402803</spage><epage>n/a</epage><pages>e202402803-n/a</pages><issn>0947-6539</issn><issn>1521-3765</issn><eissn>1521-3765</eissn><abstract>In this study, we aimed to develop protein‐based metal ligands to catalyze cis‐selective cyclopropanation using the TM1459 cupin protein superfamily. Copper complexes with TM1459 mutants containing the 3‐His metal‐binding site exhibited excellent diastereoselectivity in cyclopropanation reactions with styrene and ethyl diazoacetate. Further mutations in the secondary coordination sphere increased the cis‐preference with t‐butyl diazoacetate as the substrate with up to 80 : 20 (cis:trans ratio) and high enantioselectivity (90 % ee).
Stepwise repurposing of the first and second coordination spheres in cupin proteins yielded novel copper cupin complexes that could catalyze diastereo‐ and enantioselective cyclopropanation reactions via copper carbene species using ethyl diazoacetate. Even when employing t‐butyl diazoacetate which is too bulky to produce the cis‐cyclopropane, these nascent cyclopropanases exhibited thermodynamically unfavorable cis‐preference.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>39258820</pmid><doi>10.1002/chem.202402803</doi><tpages>5</tpages><orcidid>https://orcid.org/0000-0003-1045-6063</orcidid><orcidid>https://orcid.org/0000-0002-3711-2378</orcidid></addata></record> |
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| source | MEDLINE; Wiley Online Library Journals Frontfile Complete |
| subjects | Artificial metalloenzymes Binding Sites Catalysis Coordination Complexes - chemistry Copper Copper - chemistry Copper compounds Cupin Cyclopropanation Cyclopropanes - chemistry Enantiomers Ligands Metallocarbene Mononuclear copper enzyme Proteins Stereoisomerism Stereoselectivity Styrene Styrene - chemistry |
| title | Copper Complexes with Protein‐Based N‐Donor Ligands as cis‐Selective Nascent Cyclopropanases |
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