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CC BY 4.0 · SynOpen 2024; 08(01): 47-50
DOI: 10.1055/a-2231-3108
DOI: 10.1055/a-2231-3108
letter
tert-Butoxide-Mediated Protodeformylative Decarbonylation of α-Quaternary Homobenzaldehydes
This research was sponsored by Santa Clara University and the University of California, Merced. L.J.D. was sponsored by a summer research award from Dr. Richard Bastiani.
Abstract
tert-Butoxide mediates the Haller–Bauer-type (protodeformylative) decarbonylation of readily accessed α-quaternary homobenzaldehydes and related compounds at room temperature, generating cumene products. Both geminal dialkyl and geminal diaryl substituents are tolerated. gem-Dimethyls are sufficient for decarbonylation of polycyclic arenyl substrates whereas monocyclic aromatic homobenzaldehydes require cyclic gem-dialkyls or gem-diaryls for significant decarbonylation.
Key words
decarbonylation - C–C bond cleavage - protodeformylation - Haller–Bauer reaction - tert-butoxide - benzylic anion - cumenesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2231-3108.
- Supporting Information
Publication History
Received: 05 September 2023
Accepted after revision: 04 December 2023
Accepted Manuscript online:
18 December 2023
Article published online:
19 January 2024
© 2024. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)
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- 19 As further mechanistic support, two deuterium labeling experiments (one employing deuterated aldehyde as substrate, the other employing THF-d 8 as solvent) both afforded no detectable deuterium incorporation in the product.
- 20 See the Supporting Information for details.
- 21 Protodeformylation; General Procedure: An oven-dried 25-mL round-bottom flask was charged with a PTFE-coated magnetic stir bar, fitted with a rubber septum, and purged with nitrogen for 2 min. Then, under ambient pressure of N2, KOt-Bu solution (1.6 M in THF, 0.3 mmol, 1.6 equiv, 0.2 mL) was added to the flask, and further diluted with anhydrous THF (1.0 mL). To the flask, an anhydrous THF solution of aldehyde (0.2 M, 1.0 equiv, 1.0 mL) was added dropwise at room temperature. The mixture was then allowed to stir for 5 h under ambient pressure of N2. The reaction was diluted with EtOAc (2 mL), saturated aqueous NH4Cl (5 mL) was added, and the mixture was allowed to stir until the solution became decolored. The aqueous layer was then extracted with EtOAc (3 × 5 mL) and the combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo to afford the crude decarbonylated product, which was then purified by silica gel chromatography.
- 22 Characterization data of representative product 4b: Yield (1.0 mmol scale): 158 mg (93%); colorless oil. 1H NMR (500 MHz, CDCl3): δ = 8.16 (dd, J = 8.5, 1.2 Hz, 1 H), 7.90–7.84 (m, 1 H), 7.73 (dt, J = 7.8, 1.1 Hz, 1 H), 7.62–7.38 (m, 4 H), 3.79 (sept, J = 6.9 Hz, 1 H), 1.44 (d, J = 6.9 Hz, 6 H). 13C NMR (125 MHz, CDCl3): δ = 144.6 (C), 133.9 (C), 131.3 (C), 128.9 (CH), 126.3 (CH), 125.7 (CH), 125.6 (CH), 125.2 (CH), 123.3 (CH), 121.7 (CH), 28.5 (C), 23.6 (CH3)..
- 23 Cai X.; Stokes B. J. ChemRxiv; 2021, preprint; DOI: 10.26434/chemrxiv-2021-q22x8
For biochemical studies, see:
For decarbonylations towards biofuel conversion, see:
For the original Tsuji–Wilkinson reports, see:
For reviews, see:
Selected examples:
For a detailed overview, see:
Selected examples:
For the earliest reports of this debenzoylation, see:
For reviews of the Haller–Bauer reaction, see:
For works by Paquette and co-workers, see:
For other examples and applications, see:
For an early report of triphenylacetaldehyde deformylation using hydroxide, see:
For the original Cannizzaro disproportionation reaction, see:
For a relevant example, see:
For examples of peroxide-mediated radical decarbonylations of aldehydes, see:
For a metal-free formal (two-pot) decarbonylation of tertiary aldehydes, see:
A similar disparity between aprotic (ethereal) and protic (HOt-Bu) solvents has been observed in tert-butoxide-mediated fragmentations of ketones, see: