Journal article

Authors list: Keul, F; Mardyukov, A; Schreiner, PR

Publication year: 2022

Journal: Journal of Physical Organic Chemistry

Volume number: 35

Issue number: 11

ISSN: 0894-3230

Open access status: Hybrid

DOI Link: https://doi.org/10.1002/poc.4315

Publisher: Wiley

Abstract: 
We provide evidence for the first successful generation of phenylhydroxycarbene and 4-trifluoromethylphenylhydroxycarbene in solution. The carbene tautomers of the corresponding benzaldehyde derivatives had been prepared under cryogenic matrix-isolation conditions before but their reactivity, apart from a prototypical quantum mechanical tunneling [1,2]-H-shift reaction, had not been studied. Here our strategy is to employ suitable carbene precursors for the McFadyen-Stevens reaction, to generate the parent and the para-CF3-substituted phenylhydroxycarbenes, and to react them with benzaldehyde or acetone in a highly facile, allowed six-electron carbonyl-ene reaction toward the corresponding alpha-hydroxy ketones. Our findings are supported by computations at the DLPNO-CCSD(T)/cc-pVQZ//B3LYP/def2-TZVP level of theory.

Harvard Citation style: Keul, F., Mardyukov, A. and Schreiner, P. (2022) Generation and reactivity of phenylhydroxycarbenes in solution, Journal of Physical Organic Chemistry, 35(11), Article e4315. https://doi.org/10.1002/poc.4315

APA Citation style: Keul, F., Mardyukov, A., & Schreiner, P. (2022). Generation and reactivity of phenylhydroxycarbenes in solution. Journal of Physical Organic Chemistry. 35(11), Article e4315. https://doi.org/10.1002/poc.4315