Lemieux-Johnson氧化反應

利用OsO4/NaIO4氧化裂解碳碳雙鍵生成兩個醛的反應，稱為Lemieux-Johnson氧化。1956年，Lemieux和Johnson首先報道了此反應【Pappo, R.; Allen, D. S.; Lemieux, R. U. and Johnson, W. S., J. Org. Chem.,1956, 21, 478】。OsO4/NaIO4被稱為Lemieux-Johnson試劑，此反應也被稱為Lemieux-Johnson氧化。與臭氧化法相比，OsO4/NaIO4是一種溫和的烯烴氧化開裂法，在天然產物合成中很有用。烯烴先與OsO4反應生成鋨酸酯，再用過碘酸鈉氧化，發生開裂，在生成羰基化合物的同時，OsO4再生，所以OsO4用催化量即可。當生成的醛易于分子內縮合時，反應最好在兩相系統中進行。

在反應體系中加入2,6-二甲基吡啶可以抑制副反應，提高醛的收率【 Org. Lett. ,2004, 6, 3217】。 OsO4/Oxone作為氧化劑氧化烯烴可以直接得到兩分子羧酸。

反應機理

反應實例

To asolution of1(1.8 mg) in THF(1 mL) was addedOsO4(excess) and then a solutionof NaIO4, (excess) in H2O (1 mL). After a period of 1 hr,H2O (5 mL) was added andthe aq. solution was extracted with three 5ml portions of CHCl3. Thecombined CHCl3 layers were dried over Na2SO4,and concentrated to give a residue, which was separated by preparation TLC (SiO2,5% MeOH-CHCl3). Compounds2and3wereobtained.

【Tetrahedron,1985，41，1007-1018】.

To a solution of 100 mg 2-allyl-3-hydroxymethyl-1,4-dimethoxynaphthalene (0.4 mmol) in 5 mL water and 15 mL dioxane was first added a catalytic amount of osmium tetroxide (10 mg), and then 170 mg sodium periodate (0.8 mmol) was added portionwise over a period of 1 h. The suspension formed was stirred for 3 days, poured into water, extracted with ether, washed with brine, dried over MgSO4, and evaporated at reduced pressure. Flash chromatography on silica gel with 40% EtOAc in hexane gave 20 mg 3,4-dihydro-5,10-dimethoxy-1H-naphtho[2,3-c]pyran-3-ol, in a yield of 19%.

【J. Org. Chem.,1999, 64, 1173】

To a 0.2 M DMF solution of 4,4-dimethyl trans-stilbene was added 0.01 eq. of OsO4 (2.5% in t-BuOH) under stirring; 5 min later, 4 eq. Oxone was added in one portion, and the solution was stirred at room temperature until the solution became colorless. This usually marked the completion of the reaction which was verified by TLC. Na2SO3 (6 eq. w/w) was added to reduce the remaining oxidant, and the solution was stirred for an additional hour. EtOAc was added to extract the products and 1 N HCl was used to dissolve the salts. The organic extract was washed with 1 N HCl (3 ×) and brine and dried over Na2SO4; the solvent was removed under reduced pressure to obtain the crude product, which was purified by silica gel column chromatography to give 91% p-toluic acid.

【 J. Am. Chem. Soc. ,2002, 124, 3824】

相關文獻

1. Pappo, R.; Allen, D. S.; Lemieux, R. U. and Johnson, W. S., J. Org. Chem., 1956, 21, 478.

2. de Fatima, A. And Pilli, R. A., ARKIVOC, 2003, 118.

3. Travis, B. R.; Narayan, R. S. and Borhan, B., J. Am. Chem. Soc., 2002, 124, 3824.

4. (a) Kesteleyn, B.; de Kimpe, N. and van Puyvelde, L., J. Org. Chem., 1999, 64, 1173. (b) Vorbr¨uggen, H. and Bennua, B., Synthesis, 1985, 925.

5. Yang, D. and Zhang, C., J. Org. Chem., 2001, 66, 4814.

6. Yu, W. S.; Mei, Y.; Kang, Y.; Hua, Z. M. and Jin, Z. D., Org. Lett., 2004, 6, 3217.

7. Lee, K. Y.; Kim, Y.-H.; Han, S. B.; Kang, H. K.; Park, S. Y.; Seo, W. S.; Park, J. T.; Kim, B. S. and Chang, S. B., J. Am. Chem. Soc., 2003, 125, 6844.

8. (a) Nielsen, T. E. and Meldal, M., Org. Lett., 2005, 7, 2695. (b) De F′atima, A.; Lapis, A. A. M. and Pilli, R. A., J. Braz. Chem. Soc., 2005, 16, 495. (c) Frunzke, J.; Loschen, C. and Frenking, G., J. Am. Chem. Soc., 2004, 126, 3642. (d) Storm, J. P. and Andersson, C.-M., Org. Lett., 1999,

1, 1451. (e) Mark′o, I. E.; Mekhalfia, A.; Murphy, F.; Bayston, D. J.; Bailey, M.; Janousek, Z. and Dolan, S., Pure & Appl. Chem., 1997, 69, 565. (f) Wolfe, S.; Ingold, C. F. and Lemieux, R. U., J. Am. Chem. Soc., 1981, 103, 938.

參考資料

Comprehensive Organic Name Reactions and Reagents, by Zerong Wang，1734-1736.

相關介紹

利用Pb(OAc)4【lead tetraacetate (LTA)】氧化鄰二醇碳碳鍵斷裂得到相應的兩個羰基化合物的反應。此反應最早由Criegee在1931年報道【Criegee, R. Ber.1931, 64, 260–266】。

利用用高碘酸或高碘酸鈉，將1,2-二醇氧化斷裂得到相應的醛酮的反應，被稱為Malaprade鄰二醇氧化裂解反應。

【圖片來源：https://cheminfographic.wordpress.com/2018/01/28/70-criegee-oxidation-1931-malaprade-oxidation-1934/】