Journalartikel

Jahr der Veröffentlichung: 2010

Seiten: 1061-1069

Zeitschrift: Beilstein Journal of Organic Chemistry

Bandnummer: 6

Open Access Status: Gold

DOI Link: https://doi.org/10.3762/bjoc.6.121

Verlag: Beilstein-Institut

Abstract: 

The first C–H insertion of a hydroxycarbene species in the gas phase has been observed experimentally by means of high vacuum flash pyrolysis (HVFP) and subsequent matrix isolation: (o-Methoxyphenyl)glyoxylic acid gives non-isolable (o-methoxyphenyl)hydroxycarbene upon pyrolysis at 600 °C, which rapidly inserts into the methyl C–H bond. The insertion product, 2,3-dihydrobenzofuran-3-ol, was trapped in an excess of Ar at 11 K and characterized by infrared spectroscopy. The insertion process kinetically outruns the alternative [1,2]H-tunneling reaction to o-anisaldehyde, a type of reaction observed for other hydroxycarbenes. Traces of the dehydration product, benzo[b]furan, were also detected. The potential energy hypersurface including the insertion and hydrogen migration processes was computed at the all-electron coupled-cluster level of theory encompassing single and double substitutions and perturbatively included triple excitations [AE-CCSD(T)] in conjunction with a correlation-consistent double-ζ basis set (cc-pVDZ) by utilizing density functional theory (DFT) optimized geometries (M06-2X/cc-pVDZ) with zero-point vibrational energy (ZPVE) corrections. Exchange of the methoxy for a trifluoromethoxy group successfully prevents insertion and (o-trifluoromethoxy)benzaldehyde is produced instead; however, the carbene cannot be observed under these conditions. Thermal decomposition of (o-methoxyphenyl)glyoxylic acid in refluxing xylenes does not give the insertion product but yields o-anisaldehyde. This unanticipated outcome can be rationalized by protonation of the hydroxycarbene intermediate leading to the tautomeric formyl group. Thermochemical computations at M06-2X/cc-pVDZ in conjunction with a self-consistent solvent reaction field model support this suggested reaction pathway.

Harvard-Zitierstil: Gerbig, D., Ley, D., Reisenauer, H. and Schreiner, P. (2010) Intramolecular hydroxycarbene C–H-insertion: The curious case of (o-methoxyphenyl)hydroxycarbene, Beilstein Journal of Organic Chemistry, 6, pp. 1061-1069. https://doi.org/10.3762/bjoc.6.121

APA-Zitierstil: Gerbig, D., Ley, D., Reisenauer, H., & Schreiner, P. (2010). Intramolecular hydroxycarbene C–H-insertion: The curious case of (o-methoxyphenyl)hydroxycarbene. Beilstein Journal of Organic Chemistry. 6, 1061-1069. https://doi.org/10.3762/bjoc.6.121