在強(qiáng)酸催化下醇或烯烴與一氧化碳反應(yīng)生成多一個(gè)碳的羧酸的反應(yīng)。反應(yīng)中通常會(huì)涉及烷基的重排。由于CO操作比較麻煩，通常將甲酸加入到濃硫酸中代替。
反應(yīng)中通常涉及烷基遷移，生成熱力學(xué)更穩(wěn)定的叔碳正離子，叔碳正離子和CO反應(yīng)生成?；x子，水合生成羧酸。
【Tetrahedron Lett. 1981, 22, 2365】
2,2-Dimethylnonanoic acid (2). To 98% H2SO4 (12 mL) at 5 ℃ was added dropwise 100% formicacid (3.9 mL) over 3 min with stirring. 2-Methyl-2-nonanol 1 (795 mg, 5 mmol) in CCl4 (9 mL) wasadded during 3–5 h with stirring (100 rpm) at 5 ℃. After 5 more min, quenching with 100 g ice andextraction (Et2O) was followed by washing the extracts with 5% Na2CO3. Acidification of the basicsolution, extraction with Et2O and evaporation afforded 935 mg of 2; distillation (Kugelrohr) gave 888 mg of 2 (95%), of 95–100% purity.
【Synth. Commun. 1989, 19, 1945-1954】
1. Koch, H.; Haaf, W. Ann. 1958, 618, 251–266. 2. Hiraoka, K.; Kebarle, P. J. Am. Chem. Soc. 1977, 99, 366–370. 3. Takeuchi, K.; Akiyama, F.; Miyazaki, T.; Kitagawa, I.; Okamoto, K. Tetrahedron1987, 43, 701–709. 4. Stepanov, A. G.; Luzgin, M. V.; Romannikov, V. N.; Zamaraev, K. I. J. Am. Chem. Soc. 1995, 117, 3615–3616. 5. Olah, G. A.; Prakash, G. K. S.; Mathew, T.; Marinez, E. R. Angew. Chem. Int. Ed. 2000, 39, 2547–2548. 6. Emert, J. I.; Dankworth, D. C.; Gutierrez, A. Macromol. 2001, 34, 2766–2775. 7. Li, T.; Tsumori, N.; Souma, Y.; Xu, Q. Chem. Commun. 2003, 2070–2071. 8. Davis, M. C.; Liu, S. Synth. Commun. 2006, 36, 3509–3514. 9. Barton, V.; Ward, S. A.; Chadwick, J.; Hill, A. J. Med. Chem. 2010, 53, 4555–4559.編譯自：Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Koch–Haaf carbonylation，page 349.
