Dimerization of Indanedioneketene to Spiro-oextanone: A Theoretical Study
Indanedioneketene, a compound resulting from the thermal degradation of the phenyliodonium ylide of lawsone, dimerises quantitatively to a spiro-oxetanone derivative, a key compound for further transformations. A theoretical DFT study of this unusual for α-oxoketenes [2+2] cyclization reaction both in the gas phase and in dichloromethane solution, provides support for a) a single-step, transitionstate (involving a four-membered cyclic ring) charge controlled, concerted mechanism, and b) a [4+2] cyclization reaction, not observed but studied theoretically in this study. A parallel study of an open chain α,α'-dioxoketene dimerization explains the difference in the stability and reactivity observed experimentally between the cyclic and open chain products.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 988612
- Report Number(s):
- PNNL-SA-72271; JOCEAH; KC0301020; TRN: US201018%%572
- Journal Information:
- Journal of Organic Chemistry, Vol. 75, Issue 16; ISSN 0022-3263
- Country of Publication:
- United States
- Language:
- English
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