Dual catalytic enantioselective desymmetrization of allene-tethered cyclohexanones
The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles via an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual catalytic system, that provides synchronous activation of the cyclohexanone with a chiral prolinamide and the allene with a c...
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| Veröffentlicht in: | Chemical science (Cambridge) 2020-06, Vol.11 (28), p.7444-745 |
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| creator | Zhang, Lin Yamazaki, Ken Leitch, Jamie A Manzano, Ruben Atkinson, Victoria A. M Hamlin, Trevor A Dixon, Darren J |
| description | The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles
via
an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual catalytic system, that provides synchronous activation of the cyclohexanone with a chiral prolinamide and the allene with a copper(
i
) co-catalyst to deliver the stereodefined bicyclic core, is described. Successful application to oxygen analogues was also achieved, thereby providing a new enantioselective synthetic entry to architecturally complex bicyclic ethereal frameworks. The mechanistic pathway and the origin of enantio- and diastereoselectivities has been uncovered using density functional theory (DFT) calculations.
The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles
via
an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual prolinamide/copper(
i
) catalytic system, is described. |
| doi_str_mv | 10.1039/d0sc02878a |
| format | Article |
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via
an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual catalytic system, that provides synchronous activation of the cyclohexanone with a chiral prolinamide and the allene with a copper(
i
) co-catalyst to deliver the stereodefined bicyclic core, is described. Successful application to oxygen analogues was also achieved, thereby providing a new enantioselective synthetic entry to architecturally complex bicyclic ethereal frameworks. The mechanistic pathway and the origin of enantio- and diastereoselectivities has been uncovered using density functional theory (DFT) calculations.
The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles
via
an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual prolinamide/copper(
i
) catalytic system, is described.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/d0sc02878a</identifier><identifier>PMID: 34123026</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Allene ; Chemistry ; Crystallography ; Cyclohexanone ; Density functional theory ; Enantiomers</subject><ispartof>Chemical science (Cambridge), 2020-06, Vol.11 (28), p.7444-745</ispartof><rights>This journal is © The Royal Society of Chemistry.</rights><rights>Copyright Royal Society of Chemistry 2020</rights><rights>This journal is © The Royal Society of Chemistry 2020 The Royal Society of Chemistry</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c454t-399f16ca4642f07fd00dabfb7167f8423f9367e211252744d9f2d3ddd6f8ce453</citedby><cites>FETCH-LOGICAL-c454t-399f16ca4642f07fd00dabfb7167f8423f9367e211252744d9f2d3ddd6f8ce453</cites><orcidid>0000-0003-2456-5236 ; 0000-0003-0971-5742 ; 0000-0001-6997-184X ; 0000-0001-7290-3979 ; 0000-0002-5128-1004</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC8159440/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC8159440/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,723,776,780,860,881,27901,27902,53766,53768</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/34123026$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Zhang, Lin</creatorcontrib><creatorcontrib>Yamazaki, Ken</creatorcontrib><creatorcontrib>Leitch, Jamie A</creatorcontrib><creatorcontrib>Manzano, Ruben</creatorcontrib><creatorcontrib>Atkinson, Victoria A. M</creatorcontrib><creatorcontrib>Hamlin, Trevor A</creatorcontrib><creatorcontrib>Dixon, Darren J</creatorcontrib><title>Dual catalytic enantioselective desymmetrization of allene-tethered cyclohexanones</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><description>The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles
via
an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual catalytic system, that provides synchronous activation of the cyclohexanone with a chiral prolinamide and the allene with a copper(
i
) co-catalyst to deliver the stereodefined bicyclic core, is described. Successful application to oxygen analogues was also achieved, thereby providing a new enantioselective synthetic entry to architecturally complex bicyclic ethereal frameworks. The mechanistic pathway and the origin of enantio- and diastereoselectivities has been uncovered using density functional theory (DFT) calculations.
The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles
via
an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual prolinamide/copper(
i
) catalytic system, is described.</description><subject>Allene</subject><subject>Chemistry</subject><subject>Crystallography</subject><subject>Cyclohexanone</subject><subject>Density functional theory</subject><subject>Enantiomers</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNp9kc1LXDEUxUOxVFE33be84kaEV_P5PjaCjJ8gFNSuQya56TzJS6ZJnnT61zft6LR14d3kwvlxODcHofcEfyaY9ccGJ41p13bqDdqhmJO6Eazf2uwUb6P9lB5wGcaIoO07tM04oQzTZgfdnk3KVVpl5VZ50BV45fMQEjjQeXiEykBajSPkOPxURfBVsJVyDjzUGfICIphKr7QLC_ihfPCQ9tBbq1yC_ad3F329OL-fXdU3Xy6vZ6c3teaC55r1vSWNVrzh1OLWGoyNmtt5S5rWdpwy27OmBUoILaE5N72lhhljGttp4ILtopO173Kaj2A0-ByVk8s4jCquZFCD_F_xw0J-C4-yI6LnHBeDwyeDGL5PkLIch6TBOeUhTElSwXFb_knwgh68QB_CFH05T1JORcdE37JCHa0pHUNKEewmDMHyd1vyDN_N_rR1WuCP_8bfoM_dFODTGohJb9S_dculsYX58BrDfgECJaZe</recordid><startdate>20200624</startdate><enddate>20200624</enddate><creator>Zhang, Lin</creator><creator>Yamazaki, Ken</creator><creator>Leitch, Jamie A</creator><creator>Manzano, Ruben</creator><creator>Atkinson, Victoria A. M</creator><creator>Hamlin, Trevor A</creator><creator>Dixon, Darren J</creator><general>Royal Society of Chemistry</general><general>The Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0003-2456-5236</orcidid><orcidid>https://orcid.org/0000-0003-0971-5742</orcidid><orcidid>https://orcid.org/0000-0001-6997-184X</orcidid><orcidid>https://orcid.org/0000-0001-7290-3979</orcidid><orcidid>https://orcid.org/0000-0002-5128-1004</orcidid></search><sort><creationdate>20200624</creationdate><title>Dual catalytic enantioselective desymmetrization of allene-tethered cyclohexanones</title><author>Zhang, Lin ; Yamazaki, Ken ; Leitch, Jamie A ; Manzano, Ruben ; Atkinson, Victoria A. M ; Hamlin, Trevor A ; Dixon, Darren J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c454t-399f16ca4642f07fd00dabfb7167f8423f9367e211252744d9f2d3ddd6f8ce453</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Allene</topic><topic>Chemistry</topic><topic>Crystallography</topic><topic>Cyclohexanone</topic><topic>Density functional theory</topic><topic>Enantiomers</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zhang, Lin</creatorcontrib><creatorcontrib>Yamazaki, Ken</creatorcontrib><creatorcontrib>Leitch, Jamie A</creatorcontrib><creatorcontrib>Manzano, Ruben</creatorcontrib><creatorcontrib>Atkinson, Victoria A. M</creatorcontrib><creatorcontrib>Hamlin, Trevor A</creatorcontrib><creatorcontrib>Dixon, Darren J</creatorcontrib><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>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zhang, Lin</au><au>Yamazaki, Ken</au><au>Leitch, Jamie A</au><au>Manzano, Ruben</au><au>Atkinson, Victoria A. M</au><au>Hamlin, Trevor A</au><au>Dixon, Darren J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Dual catalytic enantioselective desymmetrization of allene-tethered cyclohexanones</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2020-06-24</date><risdate>2020</risdate><volume>11</volume><issue>28</issue><spage>7444</spage><epage>745</epage><pages>7444-745</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><abstract>The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles
via
an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual catalytic system, that provides synchronous activation of the cyclohexanone with a chiral prolinamide and the allene with a copper(
i
) co-catalyst to deliver the stereodefined bicyclic core, is described. Successful application to oxygen analogues was also achieved, thereby providing a new enantioselective synthetic entry to architecturally complex bicyclic ethereal frameworks. The mechanistic pathway and the origin of enantio- and diastereoselectivities has been uncovered using density functional theory (DFT) calculations.
The construction of enantioenriched azabicyclo[3.3.1]nonan-6-one heterocycles
via
an enantioselective desymmetrization of allene-linked cyclohexanones, enabled through a dual prolinamide/copper(
i
) catalytic system, is described.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>34123026</pmid><doi>10.1039/d0sc02878a</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0003-2456-5236</orcidid><orcidid>https://orcid.org/0000-0003-0971-5742</orcidid><orcidid>https://orcid.org/0000-0001-6997-184X</orcidid><orcidid>https://orcid.org/0000-0001-7290-3979</orcidid><orcidid>https://orcid.org/0000-0002-5128-1004</orcidid><oa>free_for_read</oa></addata></record> |
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| source | DOAJ Directory of Open Access Journals; Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals; PubMed Central; PubMed Central Open Access |
| subjects | Allene Chemistry Crystallography Cyclohexanone Density functional theory Enantiomers |
| title | Dual catalytic enantioselective desymmetrization of allene-tethered cyclohexanones |
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