Generation and Trapping of a Cage Annulated Vinylidenecarbene and Approaches to Its Cycloalkyne Isomer
A novel cage-annulated (bis-homocubyl) vinylidenecarbene has been generated and successfully trapped without any intermediacy of its cycloalkyne isomer. The greater kinetic and thermodynamic stability of the vinylidenecarbene vis-à-vis its cycloalkyne isomer has been predicted by DFT B3LYP/6-31G* c...
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| Veröffentlicht in: | Journal of organic chemistry 2012-08, Vol.77 (16), p.6998-7004 |
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| container_end_page | 7004 |
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| container_issue | 16 |
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| container_title | Journal of organic chemistry |
| container_volume | 77 |
| creator | Sahu, Bichismitha Gururaja, Guddeangadi N Kumar, Tarun Chatterjee, Anamitra Ganguly, Bishwajit Mobin, Shaikh M Namboothiri, Irishi N. N |
| description | A novel cage-annulated (bis-homocubyl) vinylidenecarbene has been generated and successfully trapped without any intermediacy of its cycloalkyne isomer. The greater kinetic and thermodynamic stability of the vinylidenecarbene vis-à-vis its cycloalkyne isomer has been predicted by DFT B3LYP/6-31G* calculations. The calculated results suggest the prospects of the cycloalkyne becoming amenable for trapping, if generated under suitable experimental conditions, owing to the substantial kinetic energy barrier associated with its possible ring contraction via 1,2-shift to the vinylidenecarbene isomer and marginal ground state energy difference. However, all of our attempts to directly generate and trap the cycloalkyne yielded unsatisfactory results. Attempted generation and trapping of a C2-symmetric bis-vinylidenecarbene from a bis-vinylidenedibromide met with unexpected failure. |
| doi_str_mv | 10.1021/jo301215d |
| format | Article |
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Attempted generation and trapping of a C2-symmetric bis-vinylidenecarbene from a bis-vinylidenedibromide met with unexpected failure.</description><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Kinetics and mechanisms</subject><subject>Organic chemistry</subject><subject>Reactivity and mechanisms</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2012</creationdate><recordtype>article</recordtype><recordid>eNpt0DtPwzAQB3ALgWh5DHwB5AUJhoAfsZOMVcSjEhILsEZX5wKB1A52MuTbY6CUBS8nWb87n_-EnHB2yZngV29OMi64qnfInCvBEl2wdJfMGRMikULLGTkI4Y3Fo5TaJzMhch6v2Zw0t2jRw9A6S8HW9NFD37f2hbqGAi3hBenC2rGDAWv63Nqpa-vYYcCvYvluWfS9d2BeMdDB0eUQaDmZzkH3PkWxDG6N_ojsNdAFPN7UQ_J0c_1Y3iX3D7fLcnGfgEzVkKRGK66V0DVvjF6BFDID2RQapZJScqNyZBqkxprHj2aZSrNMNhlyTDOGhTwk5z9z40ofI4ahWrfBYNeBRTeGijOZ8iIXjEV68UONdyF4bKret2vwU0TVV6zVNtZoTzdjx9Ua6638zTGCsw2AYKBrPFjThj-nRa4Zy_8cmBDnj97GNP558BMcLInY</recordid><startdate>20120817</startdate><enddate>20120817</enddate><creator>Sahu, Bichismitha</creator><creator>Gururaja, Guddeangadi N</creator><creator>Kumar, Tarun</creator><creator>Chatterjee, Anamitra</creator><creator>Ganguly, Bishwajit</creator><creator>Mobin, Shaikh M</creator><creator>Namboothiri, Irishi N. 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Chem</addtitle><date>2012-08-17</date><risdate>2012</risdate><volume>77</volume><issue>16</issue><spage>6998</spage><epage>7004</epage><pages>6998-7004</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>A novel cage-annulated (bis-homocubyl) vinylidenecarbene has been generated and successfully trapped without any intermediacy of its cycloalkyne isomer. The greater kinetic and thermodynamic stability of the vinylidenecarbene vis-à-vis its cycloalkyne isomer has been predicted by DFT B3LYP/6-31G* calculations. The calculated results suggest the prospects of the cycloalkyne becoming amenable for trapping, if generated under suitable experimental conditions, owing to the substantial kinetic energy barrier associated with its possible ring contraction via 1,2-shift to the vinylidenecarbene isomer and marginal ground state energy difference. However, all of our attempts to directly generate and trap the cycloalkyne yielded unsatisfactory results. 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| ispartof | Journal of organic chemistry, 2012-08, Vol.77 (16), p.6998-7004 |
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| language | eng |
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| source | ACS Publications |
| subjects | Chemistry Exact sciences and technology Kinetics and mechanisms Organic chemistry Reactivity and mechanisms |
| title | Generation and Trapping of a Cage Annulated Vinylidenecarbene and Approaches to Its Cycloalkyne Isomer |
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