Naslov
The Preparation of 7-Substituted Norbornadiene-2, 3-dicarboxylic Anhydrides and a Theoretical and Experimental Study of their Thermolysis to 5-Membered Carbocyclic or Heterocyclic Anhydrides

Autori
Margetić, Davor ; Warrener, Ronald, N, ; Sun, Guangxing ; Butler, Douglas N.

Vrsta, podvrsta i kategorija rada
Radovi u zbornicima skupova, cjeloviti rad (in extenso), znanstveni

Izvornik
The 10th International Electronic Conference on Synthetic Organic Chemistry / Http://www.usc.es/congresos/ecsoc/10/ECSOC10.htm - , 2006

Skup
The 10th International Electronic Conference on Synthetic Organic Chemistry

Mjesto i datum
Online, 01.11.2006. - 30.11.2006

Vrsta sudjelovanja
Poster

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
anhydrides; norbornenes; Diels-Alder; cycloadditions

Sažetak
Four new substituted methano-bridged or heteroatom-bridged norbornadienomaleic anhydrides have been prepared and converted to sesquinorbornadiene anhydrides by reaction with cyclic 1, 3-dienes. The versatility of parity reversal, in conjuction with N-substituent steric effects, has been used to produce all three possible stereoisomers of the N, O-sesquinorbornadiene anhydrides in separate, stereoselective cycloadditions. The anhydrides have been synthesized by cyclisation of their diacids (in situ production) or by flash vacuum pyrolysis of their furan adducts (yielding crystalline products) ; further fragmentation occurs at these or higher temperatures to produce five-membered carbocyclic or heterocyclic anhydrides. Activation energies have been evaluated for the two fragmentation processes using DFT calculations (B3LYP/6-31G*) and these calculations correctly predict which reactions can be intercepted at the norbornadienomaleic anhydride stage.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA