Mitsunobu化学反应

. To this mixture was added dropwise DIAD (0.44 mL, 2.22 mmol) over a period of 5 min, and the reaction was monitored by TLC. After complete disappearance of starting material (1 h), the solvent was evaporated under reduced pressure and the resulting oil purified by flash column chromatography (hexane/AcOEt, 8/2). Phenyl ether (0.297 g, 76%) was finally obtained as a white powder after precipitation from CH2Cl2/petroleum ether.

【 J. Org. Lett . 2004, 6, 397】

三、Mitsunobu碳替换反应不会

乙酰中间体也可以作为Mitsunobu 反应不会之前的亲连锁反应催化剂，替换羧酸，作用于替换的乙酰中间体。同样，转入反应不会的醇需要有必要的酸性（pKa

Hart和Campbell美联社2-[(trimethylsilyl)ethyl]sulfonyl（TES）保护的Boc酰醇，在Mitsunobu 乙酰替换后，可以去保护作用于Boc 保护的醇或醇的盐酸盐。

【 Synlett. 1997, 529】

【 Tetrahedron 2003, 59, 8571–8587】

【 Tetrahedron 1994, 50, 9757】

在Mitsunobu 反应不会之前用嵌碳替换羧酸，然后还原，立刻能想得到伯醇。由于嵌碳酸使用不方立刻，一个替代分析方法是用diarylphosphoryl azide(DPPA)作为嵌碳双键的来源不明。Taber 和Decher 通过这个分析方法想得到了附加的嵌碳中间体，反应不会性还亮眼。

To a cooled solution (-5o C)of DIAD (7.9 g, 93 mmol) in THF (5 mL) was added the substituted alchol (7.06g, 18.7 mmol) and PPh3 (10.3 g, 39.1 mmol). After 15 min, diphenylphosphorazidate (DPPA, 12.86 g, 46.77mmol) was added and the reaction mixturewas allowed to warm to room temperature. After stirring overnight, the solventwas removed in vacuo to give a yellow oil. The crude material was purified byflash column chromatograghy (2:1,PE/Tol) to give the desired product (7.28 g,91%) as a colorless oil.

The de-protection andhydrogenation were routine operations.

【 J. Org. Chem. 1998, 63, 4898. 】

四、 Mitsunobu硫代反应不会

活化的硫亲连锁反应催化剂也能转入Mitsunobu反应不会，作用于双手性好似的硫酯或甲酸。Merck的Volante第一次美联社了这种分析方法。

【 Tetrahedron. Lett. 1981, 22, 3119】

芳香类醇中间体都有必要的活性转入这种反应不会。

To a solution of 2-[(R)—N-(tert-butyloxycarbonyl)amino]-1-propanol(15 g, 85.6 mmol) in THF (200 mL) was added 2-mercaptobenzothiazole (14.3 g,85.6 mmol) and PPh3 (24.7 g, 94.2 mmol). After stirring for 0.25 h asolution of DEAD (14.8 mL, 94.2 mmol) in dry THF (100 mL) was added dropwiseover 0.5 h. The reaction mixture was stirred for 1 h at 20oC and filtered. Thefiltrate was evaporated and stirred with EA (100 mL), and the product wascollected by filtration (20.66 g, 74%).

【 J. Med. Chem . 1999, 42, 3463.】

五、Mitsunobu硫代反应不会

在Mitsunobu 反应不会之前，用硫氢原子替换羧酸作用于硫代物也有美联社，但其应用还不多见。Falck 等美联社了通过Mitsunobu 过程小分子一系列的硫代烃，除了氟代的反应不会性不高以外，氯代，溴代和碘代的反应不会性都亮眼。

【 Manna, S; Falck, J.R. Synth. Commun . 1985, 15, 663 】

Joulle 等美联社脯醇酸醇在经过Mitsunobu过程后想得到双手性好似的碘代游离。反应不会首先是作用于一个三氯之前间体，然后在三苯芳基的功用下发生碘代，同时双手性好似。

To a flame-driedround-bottomed flask eguipped with a magnetic stir bar and an addition funnelunder N 2 was added N-Boc-trans-4-hydroxy-L-proline methyl ester(19.29 g, 0.079 mol), triphenylphosphine (24.78 g, 0.094 mol) and anhydrous THF(2755 mL). The solution was cooled to 0 o C. Diethyl azodicarboxylate(DEAD, 14.9 mL, 0.094 mol) in anhydrous THF (15 mL) was added dropwise,followed by the addition of methyl iodide (5.88 mL, 0.094 mol). Upon additionof MeI, the solution turned from dark brown to bright yellow. The reactionmixture was allowed to warm to ambient temperature and stirred for 10 h. Thesolvent was removed under reduced pressure and the crude oil was purified bycolumn chromatograghy, eluting with 5% EA/PE to afford the desired product as awhite solid (26.22 g, 93.8%).

【 Tetrahedron: Asymm. 1998, 9, 47】

六、其他

关环

【 Tetrahedron: Asymmetry 2000, 11, 4407–4416】

碳碳键产生

特别古书

3. Kocieński, P. J.; Yeates, C.; Street, D. A.; Campbell, S. F. J. Chem. Soc., Perkin Trans. 1, 1987, 2183-2187.

4. Hughes, D. L. Org. React. 1992, 42, 335-656. (Review).

5. Hughes, D. L. Org. Prep. Proc. Int. 1996, 28, 127-164. (Review).

6. Vaccaro, W. D.; Sher, R.; Davis, H. R., Jr. Bioorg. Med. Chem. Lett. 1998, 8, 35–40.

7. Cevallos, A.; Rios, R.; Moyano, A.; Pericàs, M. A.; Riera, A. Tetrahedron: Asymmetry 2000, 11, 4407–4416.

8. Mukaiyama, T.; Shintou, T.; Fukumoto, K. J. Am. Chem. Soc. 2003, 125, 10538– 10539.

9. Sumi, S.; Matsumoto, K.; Tokuyama, H.; Fukuyama, T. Tetrahedron 2003, 59, 8571– 8587.

10. Christen, D. P. Mitsunobu reaction. In Name Reactions for Homologations-Part II; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2009, pp 671-748. (Review).

11. Ganesan, M.; Salunke, R. V.; Singh, N.; Ramesh, N. G. Org. Biomol. Chem. 2013, 11, 559-611.

参考资料

一、该网站（光延反应不会词条）

二、Strategic Applications of Named Reactions in Organic Synthesis, László Kürti and Barbara Czakó, Mitsunobu reaction, page 294.

三、药明康德宝典/Mitsunobu反应不会，谢军编著。

四、Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Mitsunobu reaction，page 407-408.

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