Organocatalytic synthesis of enantiopure spiro acenaphthyl-pyrrolizidine/pyrrolidines: justifying the regioselectivity based on a distortion/interaction model
An efficient organocatalytic [3 + 2] reaction with Schreiner's thiourea organocatalyst for the synthesis of a small library of novel enantiopure stable spiroacenaphthyl-pyrrolidines/pyrrolizidines with high regio- and diastereoselectivity (up to 99%) is described for the first time. These chira...
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| Veröffentlicht in: | Organic & biomolecular chemistry 2019-08, Vol.17 (29), p.713-724 |
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| creator | Shahrestani, Naeimeh Khosravi, Hormoz Jadidi, Khosrow Notash, Behrouz Naderi, Soheila |
| description | An efficient organocatalytic [3 + 2] reaction with Schreiner's thiourea organocatalyst for the synthesis of a small library of novel enantiopure stable spiroacenaphthyl-pyrrolidines/pyrrolizidines with high regio- and diastereoselectivity (up to 99%) is described for the first time. These chiral compounds were synthesized by a three-component 1,3-dipolar cycloaddition of (
E
)-1-(2-oxoacenaphthylen-1(2
H
)-ylidene) pyrrolidin-1-ium-2-ide as a dipolar and (
S
)-cinnamoyl/crotonoyl oxazolidinone as a dipolarophile. The absolute configuration of cycloadducts was confirmed by X-ray diffraction analysis. The origin of catalyst reactivity and regio- and stereoselectivity was investigated through DFT calculations. DFT calculations showed that the regioselectivity was controlled by the distortion (deformation) of reactants and Schreiner's thiourea acts as a LUMO-lowering catalyst.
An efficient organocatalytic synthesis of chiral spiroacenaphthyl-pyrrolidines/pyrrolizidines with high regio- and diastereoselectivity (up to 99%) with exact specification of the absolute configuration is described for the first time. |
| doi_str_mv | 10.1039/c9ob01197h |
| format | Article |
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E
)-1-(2-oxoacenaphthylen-1(2
H
)-ylidene) pyrrolidin-1-ium-2-ide as a dipolar and (
S
)-cinnamoyl/crotonoyl oxazolidinone as a dipolarophile. The absolute configuration of cycloadducts was confirmed by X-ray diffraction analysis. The origin of catalyst reactivity and regio- and stereoselectivity was investigated through DFT calculations. DFT calculations showed that the regioselectivity was controlled by the distortion (deformation) of reactants and Schreiner's thiourea acts as a LUMO-lowering catalyst.
An efficient organocatalytic synthesis of chiral spiroacenaphthyl-pyrrolidines/pyrrolizidines with high regio- and diastereoselectivity (up to 99%) with exact specification of the absolute configuration is described for the first time.</description><identifier>ISSN: 1477-0520</identifier><identifier>EISSN: 1477-0539</identifier><identifier>DOI: 10.1039/c9ob01197h</identifier><identifier>PMID: 31305857</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Absolute configuration ; Catalysis ; Catalysts ; Crystallography ; Cycloaddition ; Deformation ; Distortion ; Interaction models ; Regioselectivity ; Stereoselectivity ; Thiourea ; Thioureas ; X-ray diffraction</subject><ispartof>Organic & biomolecular chemistry, 2019-08, Vol.17 (29), p.713-724</ispartof><rights>Copyright Royal Society of Chemistry 2019</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c337t-40b2206df6dd63fe986ff58f7e93a579fac302894b0692c8465d9c7b4477e993</citedby><cites>FETCH-LOGICAL-c337t-40b2206df6dd63fe986ff58f7e93a579fac302894b0692c8465d9c7b4477e993</cites><orcidid>0000-0003-1101-1023 ; 0000-0002-6588-448X ; 0000-0003-4873-5770 ; 0000-0001-9563-3561</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27903,27904</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/31305857$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Shahrestani, Naeimeh</creatorcontrib><creatorcontrib>Khosravi, Hormoz</creatorcontrib><creatorcontrib>Jadidi, Khosrow</creatorcontrib><creatorcontrib>Notash, Behrouz</creatorcontrib><creatorcontrib>Naderi, Soheila</creatorcontrib><title>Organocatalytic synthesis of enantiopure spiro acenaphthyl-pyrrolizidine/pyrrolidines: justifying the regioselectivity based on a distortion/interaction model</title><title>Organic & biomolecular chemistry</title><addtitle>Org Biomol Chem</addtitle><description>An efficient organocatalytic [3 + 2] reaction with Schreiner's thiourea organocatalyst for the synthesis of a small library of novel enantiopure stable spiroacenaphthyl-pyrrolidines/pyrrolizidines with high regio- and diastereoselectivity (up to 99%) is described for the first time. These chiral compounds were synthesized by a three-component 1,3-dipolar cycloaddition of (
E
)-1-(2-oxoacenaphthylen-1(2
H
)-ylidene) pyrrolidin-1-ium-2-ide as a dipolar and (
S
)-cinnamoyl/crotonoyl oxazolidinone as a dipolarophile. The absolute configuration of cycloadducts was confirmed by X-ray diffraction analysis. The origin of catalyst reactivity and regio- and stereoselectivity was investigated through DFT calculations. DFT calculations showed that the regioselectivity was controlled by the distortion (deformation) of reactants and Schreiner's thiourea acts as a LUMO-lowering catalyst.
An efficient organocatalytic synthesis of chiral spiroacenaphthyl-pyrrolidines/pyrrolizidines with high regio- and diastereoselectivity (up to 99%) with exact specification of the absolute configuration is described for the first time.</description><subject>Absolute configuration</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Crystallography</subject><subject>Cycloaddition</subject><subject>Deformation</subject><subject>Distortion</subject><subject>Interaction models</subject><subject>Regioselectivity</subject><subject>Stereoselectivity</subject><subject>Thiourea</subject><subject>Thioureas</subject><subject>X-ray diffraction</subject><issn>1477-0520</issn><issn>1477-0539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNpdkUGPFCEQhYnRuOvqxbuGxIsxaYduGmi8uRN1TTaZy947NBQzTHqgBdqk_TH-1mWccUxMHXhFfXlFeAi9rsnHmlC50jIMpK6l2D1B13UrREUYlU8vuiFX6EVKe0IKw9vn6IrWlLCOiWv0exO3ygetshqX7DROi887SC7hYDF45bML0xwBp8nFgJUud9Mu75axmpYYw-h-OeM8rM7dUadPeD-n7Ozi_BYXOxxh60KCEXR2P11e8KASGBw8Vti4lEMsa_zK-QxR6aPGh2BgfImeWTUmeHU-b9DD1y8P67vqfvPt-_rzfaUpFblqydA0hBvLjeHUguy4tayzAiRVTEirNCVNJ9uBcNnoruXMSC2GtnwQSElv0PuT7RTDjxlS7g8uaRhH5SHMqW8a1tWMc0kL-u4_dB_m6MvjCsVLCUZFoT6cKB1DShFsP0V3UHHpa9IfQ-vXcnP7J7S7Ar89W87DAcwF_ZtSAd6cgJj0ZfovdfoIzwKg6Q</recordid><startdate>20190807</startdate><enddate>20190807</enddate><creator>Shahrestani, Naeimeh</creator><creator>Khosravi, Hormoz</creator><creator>Jadidi, Khosrow</creator><creator>Notash, Behrouz</creator><creator>Naderi, Soheila</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QO</scope><scope>7T7</scope><scope>7TM</scope><scope>8FD</scope><scope>C1K</scope><scope>FR3</scope><scope>P64</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-1101-1023</orcidid><orcidid>https://orcid.org/0000-0002-6588-448X</orcidid><orcidid>https://orcid.org/0000-0003-4873-5770</orcidid><orcidid>https://orcid.org/0000-0001-9563-3561</orcidid></search><sort><creationdate>20190807</creationdate><title>Organocatalytic synthesis of enantiopure spiro acenaphthyl-pyrrolizidine/pyrrolidines: justifying the regioselectivity based on a distortion/interaction model</title><author>Shahrestani, Naeimeh ; Khosravi, Hormoz ; Jadidi, Khosrow ; Notash, Behrouz ; Naderi, Soheila</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c337t-40b2206df6dd63fe986ff58f7e93a579fac302894b0692c8465d9c7b4477e993</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Absolute configuration</topic><topic>Catalysis</topic><topic>Catalysts</topic><topic>Crystallography</topic><topic>Cycloaddition</topic><topic>Deformation</topic><topic>Distortion</topic><topic>Interaction models</topic><topic>Regioselectivity</topic><topic>Stereoselectivity</topic><topic>Thiourea</topic><topic>Thioureas</topic><topic>X-ray diffraction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Shahrestani, Naeimeh</creatorcontrib><creatorcontrib>Khosravi, Hormoz</creatorcontrib><creatorcontrib>Jadidi, Khosrow</creatorcontrib><creatorcontrib>Notash, Behrouz</creatorcontrib><creatorcontrib>Naderi, Soheila</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Biotechnology Research Abstracts</collection><collection>Industrial and Applied Microbiology Abstracts (Microbiology A)</collection><collection>Nucleic Acids Abstracts</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Engineering Research Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Organic & biomolecular chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Shahrestani, Naeimeh</au><au>Khosravi, Hormoz</au><au>Jadidi, Khosrow</au><au>Notash, Behrouz</au><au>Naderi, Soheila</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Organocatalytic synthesis of enantiopure spiro acenaphthyl-pyrrolizidine/pyrrolidines: justifying the regioselectivity based on a distortion/interaction model</atitle><jtitle>Organic & biomolecular chemistry</jtitle><addtitle>Org Biomol Chem</addtitle><date>2019-08-07</date><risdate>2019</risdate><volume>17</volume><issue>29</issue><spage>713</spage><epage>724</epage><pages>713-724</pages><issn>1477-0520</issn><eissn>1477-0539</eissn><abstract>An efficient organocatalytic [3 + 2] reaction with Schreiner's thiourea organocatalyst for the synthesis of a small library of novel enantiopure stable spiroacenaphthyl-pyrrolidines/pyrrolizidines with high regio- and diastereoselectivity (up to 99%) is described for the first time. These chiral compounds were synthesized by a three-component 1,3-dipolar cycloaddition of (
E
)-1-(2-oxoacenaphthylen-1(2
H
)-ylidene) pyrrolidin-1-ium-2-ide as a dipolar and (
S
)-cinnamoyl/crotonoyl oxazolidinone as a dipolarophile. The absolute configuration of cycloadducts was confirmed by X-ray diffraction analysis. The origin of catalyst reactivity and regio- and stereoselectivity was investigated through DFT calculations. DFT calculations showed that the regioselectivity was controlled by the distortion (deformation) of reactants and Schreiner's thiourea acts as a LUMO-lowering catalyst.
An efficient organocatalytic synthesis of chiral spiroacenaphthyl-pyrrolidines/pyrrolizidines with high regio- and diastereoselectivity (up to 99%) with exact specification of the absolute configuration is described for the first time.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>31305857</pmid><doi>10.1039/c9ob01197h</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0003-1101-1023</orcidid><orcidid>https://orcid.org/0000-0002-6588-448X</orcidid><orcidid>https://orcid.org/0000-0003-4873-5770</orcidid><orcidid>https://orcid.org/0000-0001-9563-3561</orcidid></addata></record> |
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| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Absolute configuration Catalysis Catalysts Crystallography Cycloaddition Deformation Distortion Interaction models Regioselectivity Stereoselectivity Thiourea Thioureas X-ray diffraction |
| title | Organocatalytic synthesis of enantiopure spiro acenaphthyl-pyrrolizidine/pyrrolidines: justifying the regioselectivity based on a distortion/interaction model |
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