Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu3C6H2P=C: and effects of conjugation between the P=C and aromatic moieties
The intramolecular C–H insertion of the Mes*-substituted phosphanylidenecarbene [Mes*P=C:] (Mes* = 2,4,6-t-Bu3C6H2) and physicochemical properties of the cyclized product, 6,8-di-tert-butyl-3,4-dihydro-4,4-dimethyl-1-phosphanaphthalene were studied based on ab initio calculations. Whereas the altern...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2014-05-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.10.103 |
| _version_ | 1818360778564042752 |
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| author | Masaaki Yoshifuji Shigekazu Ito |
| author_facet | Masaaki Yoshifuji Shigekazu Ito |
| author_sort | Masaaki Yoshifuji |
| collection | DOAJ |
| description | The intramolecular C–H insertion of the Mes*-substituted phosphanylidenecarbene [Mes*P=C:] (Mes* = 2,4,6-t-Bu3C6H2) and physicochemical properties of the cyclized product, 6,8-di-tert-butyl-3,4-dihydro-4,4-dimethyl-1-phosphanaphthalene were studied based on ab initio calculations. Whereas the alternative Fritsch–Buttenberg–Wiechell-type rearrangement requires almost no activation energy, the intramolecular cyclization needs an activation energy of 12.3 kcal/mol at the MP2(full)/6-31G(d) condition. DFT calculations supported that the optimized structure of the cyclization product of Mes*P=C: suggests remarkable conjugation effects between the nearly coplanar P=C skeleton and the aryl moiety. |
| first_indexed | 2024-12-13T21:06:12Z |
| format | Article |
| id | doaj.art-c8fd6956e0894257b20892450ad44095 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-13T21:06:12Z |
| publishDate | 2014-05-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-c8fd6956e0894257b20892450ad440952022-12-21T23:31:29ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972014-05-011011032103610.3762/bjoc.10.1031860-5397-10-103Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu3C6H2P=C: and effects of conjugation between the P=C and aromatic moietiesMasaaki Yoshifuji0Shigekazu Ito1Department of Chemistry, Graduate School of Science, Tohoku University, Aoba, Sendai 980-8578, JapanDepartment of Chemistry, Graduate School of Science, Tohoku University, Aoba, Sendai 980-8578, JapanThe intramolecular C–H insertion of the Mes*-substituted phosphanylidenecarbene [Mes*P=C:] (Mes* = 2,4,6-t-Bu3C6H2) and physicochemical properties of the cyclized product, 6,8-di-tert-butyl-3,4-dihydro-4,4-dimethyl-1-phosphanaphthalene were studied based on ab initio calculations. Whereas the alternative Fritsch–Buttenberg–Wiechell-type rearrangement requires almost no activation energy, the intramolecular cyclization needs an activation energy of 12.3 kcal/mol at the MP2(full)/6-31G(d) condition. DFT calculations supported that the optimized structure of the cyclization product of Mes*P=C: suggests remarkable conjugation effects between the nearly coplanar P=C skeleton and the aryl moiety.https://doi.org/10.3762/bjoc.10.1033,4-dihydro-1-phosphanaphthaleneintramolecular cyclizationorganophosphorusphosphanylidenecarbenesteric protectiontheoretical calculation |
| spellingShingle | Masaaki Yoshifuji Shigekazu Ito Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu3C6H2P=C: and effects of conjugation between the P=C and aromatic moieties Beilstein Journal of Organic Chemistry 3,4-dihydro-1-phosphanaphthalene intramolecular cyclization organophosphorus phosphanylidenecarbene steric protection theoretical calculation |
| title | Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu3C6H2P=C: and effects of conjugation between the P=C and aromatic moieties |
| title_full | Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu3C6H2P=C: and effects of conjugation between the P=C and aromatic moieties |
| title_fullStr | Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu3C6H2P=C: and effects of conjugation between the P=C and aromatic moieties |
| title_full_unstemmed | Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu3C6H2P=C: and effects of conjugation between the P=C and aromatic moieties |
| title_short | Theoretical studies on the intramolecular cyclization of 2,4,6-t-Bu3C6H2P=C: and effects of conjugation between the P=C and aromatic moieties |
| title_sort | theoretical studies on the intramolecular cyclization of 2 4 6 t bu3c6h2p c and effects of conjugation between the p c and aromatic moieties |
| topic | 3,4-dihydro-1-phosphanaphthalene intramolecular cyclization organophosphorus phosphanylidenecarbene steric protection theoretical calculation |
| url | https://doi.org/10.3762/bjoc.10.103 |
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