Formation of Aza-ortho-quinone Methides Under Room Temperature Conditions: Cs 2 CO 3 Effect.
| Autor: | Walden DM; Department of Chemistry, Oregon State University , 135 Gilbert Hall, Corvallis, Oregon 97331, United States., Jaworski AA; Department of Chemistry, Northwestern University , 2145 Sheridan Rd, Evanston, Illinois 60208, United States., Johnston RC; Department of Chemistry, Oregon State University , 135 Gilbert Hall, Corvallis, Oregon 97331, United States., Hovey MT; Department of Chemistry, Northwestern University , 2145 Sheridan Rd, Evanston, Illinois 60208, United States., Baker HV; Department of Chemistry, Oregon State University , 135 Gilbert Hall, Corvallis, Oregon 97331, United States., Meyer MP; Department of Chemistry and Biochemistry, University of California , Merced, California 95453, United States., Scheidt KA; Department of Chemistry, Northwestern University , 2145 Sheridan Rd, Evanston, Illinois 60208, United States., Cheong PH; Department of Chemistry, Oregon State University , 135 Gilbert Hall, Corvallis, Oregon 97331, United States. |
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| Jazyk: | angličtina |
| Zdroj: | The Journal of organic chemistry [J Org Chem] 2017 Jul 21; Vol. 82 (14), pp. 7183-7189. Date of Electronic Publication: 2017 Jul 07. |
| DOI: | 10.1021/acs.joc.7b00697 |
| Abstrakt: | Since the first report of a facile, room temperature process to access aza-ortho-quinone methides (aoQMs) by Corey in 1999, this chemistry has remained dormant until our report of an enantioselective catalytic example in 2014. We report a theoretical and experimental study of the key to success behind these successful examples to enable broader exploitation of this useful intermediate. We have discovered that transformations involving the aoQM are remarkably facile with barriers <17 kcal/mol. The main difficulty of exploiting aoQM in synthesis is that they are unstable (ΔG > 30 kcal/mol), precluding their formation under mild conditions. The use of Cs |
| Databáze: | MEDLINE |
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