Chemistry:Allylpotassium
From HandWiki
Allylpotassium is an organopotassium compound with the molecular formula CH
2=CHCH
2K. It is a colorless, extremely air-sensitive compound that is usually generated and handled in solution. It is synthesized by metalation of propylene with Schlosser's base, a mixture of potassium tert-butoxide and butyl lithium:[1]
- CH
2=CHCH
3 + LiC
4H
9 + KOC(CH
3)
3 → KCH
2CHCH
2 + C
4H
10 + LiOC(CH
3)
3
Consistent with its extreme air-sensitivity, allylpotassium is highly nucleophilic.[2] For example, it adds to pyridine, allowing the synthesis of 4-allyl-1,4-dihydropyridines.[3] Trimethylsilyl-substituted allylpotassium have been characterized by X-ray crystallography[4]
Further reading
- Giner, J. L., Margot, C., & Djerassi,C (April 1989). "Scope and regiochemical control of the allylpotassium reaction in the synthesis of sterols with unsaturated side chains". The Journal of Organic Chemistry 54 (9): 2117–2125. doi:10.1021/jo00270a021. https://pubs.acs.org/doi/abs/10.1021/jo00270a021.
- Thompson, T. B., & Ford, W. T. (September 1979). "Rotational barriers of allyl anions in solution". Journal of the American Chemical Society 101 (19): 5459–5464. doi:10.1021/ja00513a001. Bibcode: 1979JAChS.101.5459T. https://pubs.acs.org/doi/abs/10.1021/ja00513a001.
References
- ↑ Schlosser, M. (1974). "Prescriptions and Ingredients for Controlled CC Bond Formation with Organometallic Reagents. New synthetic methods". Angewandte Chemie International Edition in English 13 (11): 701–706. doi:10.1002/anie.197407011. http://infoscience.epfl.ch/record/81494.
- ↑ Zhang, X., Fensterbank, L., & Chauvier, C. (15 December 2023). "Silylation of Allylic C(sp3 )–H Bonds Enabled by the Catalytic Generation of Allylpotassium Complexes". ACS Catalysis 13 (24): 16207–16214. doi:10.1021/acscatal.3c04626. https://pubs.acs.org/doi/10.1021/acscatal.3c04626.
- ↑ Schlosser, M (1 January 1988). "Superbases for organic synthesis". Pure and Applied Chemistry 60 (11): 1627–1634. doi:10.1351/pac198860111627. https://www.degruyter.com/document/doi/10.1351/pac198860111627/html.
- ↑ Sulway, S. A., Girshfeld, R., Solomon, S. A., Muryn, C. A., Poater, J., Solà, M., Bickelhaupt, F. M., & Layfield, R. A. (September 2009). "Alkali Metal Complexes of Silyl-Substituted ansa -(Tris)allyl Ligands: Metal-, Co-Ligand- and Substituent-Dependent Stereochemistry". European Journal of Inorganic Chemistry (27): 4157–4167. doi:10.1002/ejic.200900618. https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.200900618.
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