Development of Chiral Nucleophilic Pyridine Catalysts: Applications in Asymmetric Quaternary Carbon Synthesis
TADMAP (1a), a new chiral DMAP catalyst, has been designed to place a C(3)-benzylic trityl group over one face of the pyridine ring, while a C(3)-benzylic acetoxy group creates a chirotopic environment on the other face. TADMAP was prepared in four steps (37% overall) from triphenylacetic acid and (...
Gespeichert in:
| Veröffentlicht in: | Journal of the American Chemical Society 2003-11, Vol.125 (44), p.13368-13369 |
|---|---|
| Hauptverfasser: | , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 13369 |
|---|---|
| container_issue | 44 |
| container_start_page | 13368 |
| container_title | Journal of the American Chemical Society |
| container_volume | 125 |
| creator | Shaw, Scott A Aleman, Pedro Vedejs, Edwin |
| description | TADMAP (1a), a new chiral DMAP catalyst, has been designed to place a C(3)-benzylic trityl group over one face of the pyridine ring, while a C(3)-benzylic acetoxy group creates a chirotopic environment on the other face. TADMAP was prepared in four steps (37% overall) from triphenylacetic acid and (dimethylamino)pyridine and was resolved using camphorsulfonic acid. TADMAP catalyzes the enantioselective rearrangement from oxazolyl phenyl carbonates 4 to azlactones 5, from furanyl phenyl carbonate 8 to the furanone 9, from the benzofuranyl carbonates 11a and 11b to benzofuranones 12a and 12b, and from the indolyl carbonates 11c and 11d to oxindoles 12c and 12d. The products are formed in good yield and, in most cases, with practical levels of enantiomer excess at the newly formed quaternary carbon. |
| doi_str_mv | 10.1021/ja037223k |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_71318256</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>71318256</sourcerecordid><originalsourceid>FETCH-LOGICAL-a445t-3a0d2146cb42143011b48bdddb96d3b36bfc760db106e60cda1b16aed9f49e263</originalsourceid><addsrcrecordid>eNptkUtvEzEUhS0EoqGw4A8gb0BiMeDHjGfCLgqPIpXSKqViZ_k1ilPPA18PYnZs-Zv8Elwlajasrq7Od4-OzkXoOSVvKGH07U4RXjPGbx-gBa0YKSrKxEO0IISwom4EP0FPAHZ5LVlDH6MTWlYNJ6xeoPG9--nCMHauT3ho8Xrrowr4YjLBDePWB2_w5Ry99b3Da5VUmCHBu7-__-DVOGZVJT_0gH2PVzB3nUsxX1xNKrnYqzjnm6iHHm_mPm0deHiKHrUqgHt2mKfo28cP1-uz4vzrp8_r1XmhyrJKBVfEMloKo8s8OKFUl4221uqlsFxzoVtTC2I1JcIJYqyimgrl7LItl44Jfope7X3HOPyYHCTZeTAuBNW7YQJZU04bVt2Br_egiQNAdK0co-9ydEmJvKtX3teb2RcH00l3zh7JQ58ZeHkAFBgV2qh64-HIVUzQ_IPMFXvOQ3K_7nUVb6WoeV3J68uN_H71ZVPdXNzIs6OvMiB3w5S7DfCfgP8Ak5-gKA</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>71318256</pqid></control><display><type>article</type><title>Development of Chiral Nucleophilic Pyridine Catalysts: Applications in Asymmetric Quaternary Carbon Synthesis</title><source>ACS Publications</source><creator>Shaw, Scott A ; Aleman, Pedro ; Vedejs, Edwin</creator><creatorcontrib>Shaw, Scott A ; Aleman, Pedro ; Vedejs, Edwin</creatorcontrib><description>TADMAP (1a), a new chiral DMAP catalyst, has been designed to place a C(3)-benzylic trityl group over one face of the pyridine ring, while a C(3)-benzylic acetoxy group creates a chirotopic environment on the other face. TADMAP was prepared in four steps (37% overall) from triphenylacetic acid and (dimethylamino)pyridine and was resolved using camphorsulfonic acid. TADMAP catalyzes the enantioselective rearrangement from oxazolyl phenyl carbonates 4 to azlactones 5, from furanyl phenyl carbonate 8 to the furanone 9, from the benzofuranyl carbonates 11a and 11b to benzofuranones 12a and 12b, and from the indolyl carbonates 11c and 11d to oxindoles 12c and 12d. The products are formed in good yield and, in most cases, with practical levels of enantiomer excess at the newly formed quaternary carbon.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja037223k</identifier><identifier>PMID: 14583027</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Chemical reactivity ; Chemistry ; Exact sciences and technology ; Organic chemistry ; Reactivity and mechanisms</subject><ispartof>Journal of the American Chemical Society, 2003-11, Vol.125 (44), p.13368-13369</ispartof><rights>Copyright © 2003 American Chemical Society</rights><rights>2004 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a445t-3a0d2146cb42143011b48bdddb96d3b36bfc760db106e60cda1b16aed9f49e263</citedby><cites>FETCH-LOGICAL-a445t-3a0d2146cb42143011b48bdddb96d3b36bfc760db106e60cda1b16aed9f49e263</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja037223k$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja037223k$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>315,781,785,2766,27081,27929,27930,56743,56793</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=15261428$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/14583027$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Shaw, Scott A</creatorcontrib><creatorcontrib>Aleman, Pedro</creatorcontrib><creatorcontrib>Vedejs, Edwin</creatorcontrib><title>Development of Chiral Nucleophilic Pyridine Catalysts: Applications in Asymmetric Quaternary Carbon Synthesis</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>TADMAP (1a), a new chiral DMAP catalyst, has been designed to place a C(3)-benzylic trityl group over one face of the pyridine ring, while a C(3)-benzylic acetoxy group creates a chirotopic environment on the other face. TADMAP was prepared in four steps (37% overall) from triphenylacetic acid and (dimethylamino)pyridine and was resolved using camphorsulfonic acid. TADMAP catalyzes the enantioselective rearrangement from oxazolyl phenyl carbonates 4 to azlactones 5, from furanyl phenyl carbonate 8 to the furanone 9, from the benzofuranyl carbonates 11a and 11b to benzofuranones 12a and 12b, and from the indolyl carbonates 11c and 11d to oxindoles 12c and 12d. The products are formed in good yield and, in most cases, with practical levels of enantiomer excess at the newly formed quaternary carbon.</description><subject>Chemical reactivity</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Organic chemistry</subject><subject>Reactivity and mechanisms</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2003</creationdate><recordtype>article</recordtype><recordid>eNptkUtvEzEUhS0EoqGw4A8gb0BiMeDHjGfCLgqPIpXSKqViZ_k1ilPPA18PYnZs-Zv8Elwlajasrq7Od4-OzkXoOSVvKGH07U4RXjPGbx-gBa0YKSrKxEO0IISwom4EP0FPAHZ5LVlDH6MTWlYNJ6xeoPG9--nCMHauT3ho8Xrrowr4YjLBDePWB2_w5Ry99b3Da5VUmCHBu7-__-DVOGZVJT_0gH2PVzB3nUsxX1xNKrnYqzjnm6iHHm_mPm0deHiKHrUqgHt2mKfo28cP1-uz4vzrp8_r1XmhyrJKBVfEMloKo8s8OKFUl4221uqlsFxzoVtTC2I1JcIJYqyimgrl7LItl44Jfope7X3HOPyYHCTZeTAuBNW7YQJZU04bVt2Br_egiQNAdK0co-9ydEmJvKtX3teb2RcH00l3zh7JQ58ZeHkAFBgV2qh64-HIVUzQ_IPMFXvOQ3K_7nUVb6WoeV3J68uN_H71ZVPdXNzIs6OvMiB3w5S7DfCfgP8Ak5-gKA</recordid><startdate>20031105</startdate><enddate>20031105</enddate><creator>Shaw, Scott A</creator><creator>Aleman, Pedro</creator><creator>Vedejs, Edwin</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20031105</creationdate><title>Development of Chiral Nucleophilic Pyridine Catalysts: Applications in Asymmetric Quaternary Carbon Synthesis</title><author>Shaw, Scott A ; Aleman, Pedro ; Vedejs, Edwin</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a445t-3a0d2146cb42143011b48bdddb96d3b36bfc760db106e60cda1b16aed9f49e263</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2003</creationdate><topic>Chemical reactivity</topic><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>Organic chemistry</topic><topic>Reactivity and mechanisms</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Shaw, Scott A</creatorcontrib><creatorcontrib>Aleman, Pedro</creatorcontrib><creatorcontrib>Vedejs, Edwin</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Shaw, Scott A</au><au>Aleman, Pedro</au><au>Vedejs, Edwin</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Development of Chiral Nucleophilic Pyridine Catalysts: Applications in Asymmetric Quaternary Carbon Synthesis</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2003-11-05</date><risdate>2003</risdate><volume>125</volume><issue>44</issue><spage>13368</spage><epage>13369</epage><pages>13368-13369</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>TADMAP (1a), a new chiral DMAP catalyst, has been designed to place a C(3)-benzylic trityl group over one face of the pyridine ring, while a C(3)-benzylic acetoxy group creates a chirotopic environment on the other face. TADMAP was prepared in four steps (37% overall) from triphenylacetic acid and (dimethylamino)pyridine and was resolved using camphorsulfonic acid. TADMAP catalyzes the enantioselective rearrangement from oxazolyl phenyl carbonates 4 to azlactones 5, from furanyl phenyl carbonate 8 to the furanone 9, from the benzofuranyl carbonates 11a and 11b to benzofuranones 12a and 12b, and from the indolyl carbonates 11c and 11d to oxindoles 12c and 12d. The products are formed in good yield and, in most cases, with practical levels of enantiomer excess at the newly formed quaternary carbon.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>14583027</pmid><doi>10.1021/ja037223k</doi><tpages>2</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0002-7863 |
| ispartof | Journal of the American Chemical Society, 2003-11, Vol.125 (44), p.13368-13369 |
| issn | 0002-7863 1520-5126 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_71318256 |
| source | ACS Publications |
| subjects | Chemical reactivity Chemistry Exact sciences and technology Organic chemistry Reactivity and mechanisms |
| title | Development of Chiral Nucleophilic Pyridine Catalysts: Applications in Asymmetric Quaternary Carbon Synthesis |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-11T15%3A37%3A49IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Development%20of%20Chiral%20Nucleophilic%20Pyridine%20Catalysts:%E2%80%89%20Applications%20in%20Asymmetric%20Quaternary%20Carbon%20Synthesis&rft.jtitle=Journal%20of%20the%20American%20Chemical%20Society&rft.au=Shaw,%20Scott%20A&rft.date=2003-11-05&rft.volume=125&rft.issue=44&rft.spage=13368&rft.epage=13369&rft.pages=13368-13369&rft.issn=0002-7863&rft.eissn=1520-5126&rft.coden=JACSAT&rft_id=info:doi/10.1021/ja037223k&rft_dat=%3Cproquest_cross%3E71318256%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=71318256&rft_id=info:pmid/14583027&rfr_iscdi=true |