Iminophosphorane Mediated Imine Metathesis
The iminophosphorane Cl3PNAr (1a, Ar = 2-fluorophenyl) reacts metathetically with imines at 80 °C to produce NR exchange products. Compound 1a effectively catalyzes imine/imine and imine/carbodiimide cross-metathesis. The observation of NR exchange products as well as spectroscopic evidence for t...
Saved in:
| Published in | Inorganic chemistry Vol. 42; no. 11; pp. 3438 - 3444 |
|---|---|
| Main Authors | , |
| Format | Journal Article |
| Language | English |
| Published |
United States
American Chemical Society
02.06.2003
|
| Online Access | Get full text |
Cover
Loading…
| Abstract | The iminophosphorane Cl3PNAr (1a, Ar = 2-fluorophenyl) reacts metathetically with imines at 80 °C to produce NR exchange products. Compound 1a effectively catalyzes imine/imine and imine/carbodiimide cross-metathesis. The observation of NR exchange products as well as spectroscopic evidence for the existence of diazaphosphetidine type intermediates suggests that a [2 + 2] addition/elimination mechanism is the primary pathway for substrates with N-alkyl substituents and a secondary pathway for N-aryl imines. In contrast to previously studied carbodiimide systems, the resting state of the catalyst is the iminophosphorane and not the diazaphosphetidine. For N-aryl imines, Lewis-acid catalysis appears to be the dominant mechanism, not addition/elimination. For N-alkyl imines, a decomposition pathway, involving HCl elimination from a phosphorus intermediate, is competitive in some cases. |
|---|---|
| AbstractList | The iminophosphorane Cl(3)P[double bond]NAr (1a, Ar = 2-fluorophenyl) reacts metathetically with imines at 80 degrees C to produce [double bond]NR exchange products. Compound 1a effectively catalyzes imine/imine and imine/carbodiimide cross-metathesis. The observation of [double bond]NR exchange products as well as spectroscopic evidence for the existence of diazaphosphetidine type intermediates suggests that a [2 + 2] addition/elimination mechanism is the primary pathway for substrates with N-alkyl substituents and a secondary pathway for N-aryl imines. In contrast to previously studied carbodiimide systems, the resting state of the catalyst is the iminophosphorane and not the diazaphosphetidine. For N-aryl imines, Lewis-acid catalysis appears to be the dominant mechanism, not addition/elimination. For N-alkyl imines, a decomposition pathway, involving HCl elimination from a phosphorus intermediate, is competitive in some cases. The iminophosphorane Cl3PNAr (1a, Ar = 2-fluorophenyl) reacts metathetically with imines at 80 °C to produce NR exchange products. Compound 1a effectively catalyzes imine/imine and imine/carbodiimide cross-metathesis. The observation of NR exchange products as well as spectroscopic evidence for the existence of diazaphosphetidine type intermediates suggests that a [2 + 2] addition/elimination mechanism is the primary pathway for substrates with N-alkyl substituents and a secondary pathway for N-aryl imines. In contrast to previously studied carbodiimide systems, the resting state of the catalyst is the iminophosphorane and not the diazaphosphetidine. For N-aryl imines, Lewis-acid catalysis appears to be the dominant mechanism, not addition/elimination. For N-alkyl imines, a decomposition pathway, involving HCl elimination from a phosphorus intermediate, is competitive in some cases. |
| Author | Burland, Matthew C Meyer, Tara Y |
| Author_xml | – sequence: 1 givenname: Matthew C surname: Burland fullname: Burland, Matthew C – sequence: 2 givenname: Tara Y surname: Meyer fullname: Meyer, Tara Y |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/12767179$$D View this record in MEDLINE/PubMed |
| BookMark | eNptkEtLAzEQx4NU7EMPfgHpRUFhdZJsks1Rio9CfdFavIVsNku3trs12QX99qZsqRcPw8zw_zGPfx91yqq0CJ1iuMZA8E1hgHCKaXKAepgRiBiGjw7qAYQacy67qO_9EgAkjfkR6mIiuMBC9tDVeF2U1WZR-RBOl3b4ZLNC1zYbbpVtW-t6YX3hj9FhrlfenuzyAL3f381Gj9Hk5WE8up1EmsayjlKaE8ZpwlJCdZaCMSBiLpkBw3JNSU5imiQ5IXFCbJyamOfY2oRrnmUMNKEDdNHO3bjqq7G-VuvCG7taheuqxitBiaQyPDxAly1oXOW9s7nauGKt3Y_CoLbGqL0xgT3bDW3Stc3-yJ0TAYhaoPC1_d7r2n0qLqhgavY6VXMhpxM5f1ZvgT9veW28WlaNK4Mn_yz-BRq8eOg |
| CitedBy_id | crossref_primary_10_1021_ja900256g crossref_primary_10_1021_acscatal_3c04135 crossref_primary_10_1021_om500268x crossref_primary_10_1021_ic0700351 crossref_primary_10_1039_B912783F crossref_primary_10_1021_jo049250e crossref_primary_10_1021_om070154o crossref_primary_10_1039_C8SC00929E crossref_primary_10_1039_D2DT02855G crossref_primary_10_1021_om201012g crossref_primary_10_1039_b417713d crossref_primary_10_1039_b501827g crossref_primary_10_1039_D2QO01638A crossref_primary_10_1002_ejoc_201001372 crossref_primary_10_1021_ic0607888 crossref_primary_10_1002_ejic_200400318 crossref_primary_10_1002_chem_200601452 crossref_primary_10_1021_ic050230k crossref_primary_10_1002_ange_201803797 crossref_primary_10_1021_ic050203u crossref_primary_10_1002_anie_201803797 crossref_primary_10_1039_b719361k |
| Cites_doi | 10.1021/om9708889 10.1021/om011085v 10.1021/om011086n 10.1002/zaac.19663430307 |
| ContentType | Journal Article |
| Copyright | Copyright © 2003 American Chemical Society |
| Copyright_xml | – notice: Copyright © 2003 American Chemical Society |
| DBID | BSCLL NPM AAYXX CITATION 7X8 |
| DOI | 10.1021/ic0263138 |
| DatabaseName | Istex PubMed CrossRef MEDLINE - Academic |
| DatabaseTitle | PubMed CrossRef MEDLINE - Academic |
| DatabaseTitleList | MEDLINE - Academic PubMed |
| Database_xml | – sequence: 1 dbid: NPM name: PubMed url: https://proxy.k.utb.cz/login?url=http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed sourceTypes: Index Database |
| DeliveryMethod | fulltext_linktorsrc |
| Discipline | Chemistry |
| EISSN | 1520-510X |
| EndPage | 3444 |
| ExternalDocumentID | 10_1021_ic0263138 12767179 ark_67375_TPS_V79SL9VN_Q c33540477 |
| Genre | Journal Article |
| GroupedDBID | - .K2 02 186 4.4 53G 55A 5GY 5VS 7~N 85S AABXI ABDEX ABFLS ABMVS ABPPZ ABPTK ABUCX ABUFD ACGFS ACJ ACNCT ACS ADKFC AEESW AENEX AETEA AFEFF AFFNX AFMIJ AIDAL ALMA_UNASSIGNED_HOLDINGS ANTXH AQSVZ BAANH CS3 D0L DU5 DZ EBS ED ED~ EJD F20 F5P GNL H~9 IH9 IHE JG JG~ K2 LG6 MVM NHB OHT ROL RXW TAE TN5 TWZ UI2 UKR UNC UPT UQL VF5 VG9 VQA VQP W1F WH7 X XFK YZZ ZCG ZHY --- -DZ -~X 6TJ AAYOK ABJNI ABQRX ADHLV AGXLV AHGAQ BSCLL CUPRZ GGK IH2 XOL XSW ~02 NPM AAYXX CITATION 7X8 |
| ID | FETCH-LOGICAL-a349t-b3f256385b23adb0cc074695c0c5fa32f24388f22482e4bc46f1ee86a6dd50a23 |
| IEDL.DBID | ACS |
| ISSN | 0020-1669 |
| IngestDate | Fri Oct 25 04:40:57 EDT 2024 Thu Sep 26 16:27:25 EDT 2024 Sat Sep 28 07:40:15 EDT 2024 Wed Oct 30 09:42:09 EDT 2024 Thu Aug 27 13:42:49 EDT 2020 |
| IsPeerReviewed | true |
| IsScholarly | true |
| Issue | 11 |
| Language | English |
| LinkModel | DirectLink |
| MergedId | FETCHMERGED-LOGICAL-a349t-b3f256385b23adb0cc074695c0c5fa32f24388f22482e4bc46f1ee86a6dd50a23 |
| Notes | istex:A443D64FBA1A11F4FBD3CD419E4548DC07507D46 ark:/67375/TPS-V79SL9VN-Q ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| PMID | 12767179 |
| PQID | 73293926 |
| PQPubID | 23479 |
| PageCount | 7 |
| ParticipantIDs | proquest_miscellaneous_73293926 crossref_primary_10_1021_ic0263138 pubmed_primary_12767179 istex_primary_ark_67375_TPS_V79SL9VN_Q acs_journals_10_1021_ic0263138 |
| ProviderPackageCode | JG~ 55A AABXI GNL VF5 7~N ACJ VG9 W1F ANTXH ACS AEESW AFEFF .K2 ABMVS ABUCX IH9 BAANH AQSVZ ED~ UI2 |
| PublicationCentury | 2000 |
| PublicationDate | 2003-06-02 |
| PublicationDateYYYYMMDD | 2003-06-02 |
| PublicationDate_xml | – month: 06 year: 2003 text: 2003-06-02 day: 02 |
| PublicationDecade | 2000 |
| PublicationPlace | United States |
| PublicationPlace_xml | – name: United States |
| PublicationTitle | Inorganic chemistry |
| PublicationTitleAlternate | Inorg. Chem |
| PublicationYear | 2003 |
| Publisher | American Chemical Society |
| Publisher_xml | – name: American Chemical Society |
| References | Blackwell J. M. (ic0263138b00012/ic0263138b00012_1) 2002; 21 ic0263138b00001/ic0263138b00001_1 Meyer K. E. (ic0263138b00004/ic0263138b00004_1) 1994; 116 Bell S. A. (ic0263138b00007/ic0263138b00007_1) 2002; 124 Becke-Goehring M. (ic0263138b00010/ic0263138b00010_1) 1966; 343 Cantrell G. K. (ic0263138b00003/ic0263138b00003_1) 1997; 16 Bell S. A. (ic0263138b00008/ic0263138b00008_1) 2000; 1375 Jordan R. F. (ic0263138b00005/ic0263138b00005_1) 1997; 119 Johnson A. (ic0263138b00006/ic0263138b00006_1) 1993 Burland M. C. (ic0263138b00002/ic0263138b00002_1) 2002; 21 Toth G. (ic0263138b00013/ic0263138b00013_1) 1974; 9 |
| References_xml | – volume: 119 start-page: 8126 year: 1997 ident: ic0263138b00005/ic0263138b00005_1 publication-title: J. Am. Chem. Soc. contributor: fullname: Jordan R. F. – volume: 116 start-page: 2670 year: 1994 ident: ic0263138b00004/ic0263138b00004_1 publication-title: J. Am. Chem. Soc. contributor: fullname: Meyer K. E. – volume: 1375 start-page: 1376 year: 2000 ident: ic0263138b00008/ic0263138b00008_1 publication-title: J. Chem. Soc., Chem. Commun. contributor: fullname: Bell S. A. – volume: 16 start-page: 5383 year: 1997 ident: ic0263138b00003/ic0263138b00003_1 publication-title: Organometallics doi: 10.1021/om9708889 contributor: fullname: Cantrell G. K. – volume: 21 start-page: 1941 year: 2002 ident: ic0263138b00002/ic0263138b00002_1 publication-title: Organometallics doi: 10.1021/om011085v contributor: fullname: Burland M. C. – volume: 21 start-page: 1407 year: 2002 ident: ic0263138b00012/ic0263138b00012_1 publication-title: Organometallics doi: 10.1021/om011086n contributor: fullname: Blackwell J. M. – volume: 9 start-page: 738 year: 1974 ident: ic0263138b00013/ic0263138b00013_1 publication-title: Tetrahedron Lett. contributor: fullname: Toth G. – volume: 343 start-page: 164 year: 1966 ident: ic0263138b00010/ic0263138b00010_1 publication-title: Z. Anorg. Allg. Chem. doi: 10.1002/zaac.19663430307 contributor: fullname: Becke-Goehring M. – volume: 124 start-page: 10705 year: 2002 ident: ic0263138b00007/ic0263138b00007_1 publication-title: J. Am. Chem. Soc. contributor: fullname: Bell S. A. – ident: ic0263138b00001/ic0263138b00001_1 – start-page: 305 volume-title: Ylides and Imines of Phosphorus year: 1993 ident: ic0263138b00006/ic0263138b00006_1 contributor: fullname: Johnson A. |
| SSID | ssj0009346 |
| Score | 1.883 |
| Snippet | The iminophosphorane Cl3PNAr (1a, Ar = 2-fluorophenyl) reacts metathetically with imines at 80 °C to produce NR exchange products. Compound 1a effectively... The iminophosphorane Cl(3)P[double bond]NAr (1a, Ar = 2-fluorophenyl) reacts metathetically with imines at 80 degrees C to produce [double bond]NR exchange... |
| SourceID | proquest crossref pubmed istex acs |
| SourceType | Aggregation Database Index Database Publisher |
| StartPage | 3438 |
| Title | Iminophosphorane Mediated Imine Metathesis |
| URI | http://dx.doi.org/10.1021/ic0263138 https://api.istex.fr/ark:/67375/TPS-V79SL9VN-Q/fulltext.pdf https://www.ncbi.nlm.nih.gov/pubmed/12767179 https://search.proquest.com/docview/73293926 |
| Volume | 42 |
| hasFullText | 1 |
| inHoldings | 1 |
| isFullTextHit | |
| isPrint | |
| link | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwhV1ZS8QwEB48HvTF-1jPRcUHodrmavIoq6KioqyKbyFJE1zEXbFdEH-9Sbv1wOuhD6UpTWcGvm-YzHwAW8gx6mKaRUQxHBGiTKQpx5FNuGUm8XlQ2fV-fsGOb8jpHb0bgs1fKvgo2esYnybgBPNhGEVpLII-w36r_TFZF1fdOCEPShgT9figz68G6DH5F-gZDVZ8-Z1XlvhyNAkHdZdOdazkYbdf6F3z-n1o419bn4KJAb9s7lcBMQ1DtjsDY61a1m0Wdk4eO93e030v95cHKts8L9U6bNYMT8JtEVhh3snn4Obo8Lp1HA0EEyKFiSgijZ1nMJhTjbDKdGxMUBMR1MSGOoWRQwRz7jxqc2SJNoS5xFrOFMsyGiuE52Gk2-vaRWh61oRUyhhxiSaWauFxjBvsMqeto9g0YM1bVA4CPpdlLRsl8v2XG7BRG1s-VYMzflq0XbrhfYV6fggnzVIqry_b8jYV7TNxeyGvGrBe-0l6e4WihjdQr5_LFHvCIhBrwELlvo-voZT5ZFUs_bfVZRhHlahiFKMVGCme-3bVU41Cr5Wh9gaxAcjT |
| link.rule.ids | 315,783,787,2774,27090,27938,27939,57072,57122 |
| linkProvider | American Chemical Society |
| linkToHtml | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwjV3Na9swFH90zaG7bOvWdlm7Joyxw8CtrS_LxxIW0i4JHUlLb0KSJRrCnFI7MPbXT5LjZB0r7cEHY9l-H4L3ezy99wP4jCyjNqZ5RCTDESFSR4pyHJmEG6YTlweFrvfRmA2uyMUNvVmNyfG9ME6I0n2pDEX8zXSB5HSmXbaAE8xfQIumcerZCs56k82AXVw35fh0KGEsa6YI_f2qj0C6fBCBWt6Yvx6HlyHM9F_XfEVBwHC6ZH6yrNSJ_v3P7MbnafAGXq3QZves3h67sGWKt7DTa0je3sHX85-zYnF3uyjd5cKW6Y4Cd4fJu_6Jv608Rixn5R5c9b9Ne4NoRZ8QSUyyKlLYOjyDOVUIy1zFWntukYzqWFMrMbKIYM6ti-EcGaI0YTYxhjPJ8pzGEuF92C4WhXkPXYehkEwZIzZRxFCVuajGNba5VcZSrNtw7DQWq-1filDZRolYq9yGT43NxV09RuN_i74Eb6xXyPu5P3eWUjG9nIjrNJsMs-ux-NGGTuMu4ezlSxzOQItlKVLs4EuGWBsOai9u_oZS5lLX7MNTonZgZzAdDcXwfPz9EF6imm4xitERbFf3S_PRgZBKHYfd9wfxStE8 |
| linkToPdf | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwjV1LT-MwEB6xILFcgH1BeVYI7WGlsPEzzhEVKliggAqIm2U7tqgQbUVSCfHrsZO0LAgEhxyiOMl4xtb3jcYzA7CNHWcuZllEFScRpcpEmgkSWSQsN8j7QWXW-0mHH1zSf9fsunYUQy6MFyL3X8rLIH7Y1cPM1RUG0N-e8R4DQUR8gRmWIBw6Fuy2us9FdkmVmBNcIsR5Oq4k9P-rAYVM_gKFZoJCH96nmCXUtBfgdCJkecLkdmdU6B3z-Kp-4-dnsQjzNets7lbL5BtM2f53-NoaN3v7AX8O73r9wfBmkPvLw5dtnpQ9PGzWDE_CbRG4Yt7Lf8Jle_-idRDVbRQiRWhaRJo4z2uIYBoTlenYmNBjJGUmNswpgh2mRAjnsVxgS7Wh3CFrBVc8y1isMPkF0_1B3y5D03MprBLOqUOaWqZTj27CEJc5bR0jpgEbftay3ga5LCPcGMnJlBuwNda7HFblNN4a9Lu0yGSEur8N588SJi_OuvIqSbvH6VVHnjdgc2wy6fUVQh1eQYNRLhPiaUyKeQOWKks-_w0n3Luw6cpHom7C7NleWx4fdo5WYQ5XXRejGK_BdHE_suueixR6o1yAT-w907Y |
| openUrl | ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Iminophosphorane+Mediated+Imine+Metathesis&rft.jtitle=Inorganic+chemistry&rft.au=Burland%2C+Matthew+C.&rft.au=Meyer%2C+Tara+Y.&rft.date=2003-06-02&rft.issn=0020-1669&rft.eissn=1520-510X&rft.volume=42&rft.issue=11&rft.spage=3438&rft.epage=3444&rft_id=info:doi/10.1021%2Fic0263138&rft.externalDBID=n%2Fa&rft.externalDocID=10_1021_ic0263138 |
| thumbnail_l | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/lc.gif&issn=0020-1669&client=summon |
| thumbnail_m | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/mc.gif&issn=0020-1669&client=summon |
| thumbnail_s | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/sc.gif&issn=0020-1669&client=summon |