Mitsunobu加成

under a nitrogen atmosphere. 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碳改用反应则会

酰衍生物也可以作为Mitsunobu 反应则会中所的亲连锁反应阴离子，改用甲基，分解改用的酰衍生物。同样，参加反应则会的醯不能有所需的醇病态（pKa

Hart和Campbell华盛顿邮报2-[(trimethylsilyl)ethyl]sulfonyl（TES）庇护所的Boc酰醯，在Mitsunobu 酰改用后，可以去庇护所分解Boc 庇护所的醯或醯的盐醇盐。

【 Synlett. 1997, 529】

【 Tetrahedron 2003, 59, 8571–8587】

【 Tetrahedron 1994, 50, 9757】

在Mitsunobu 反应则会中所用亚硝醇改用甲基，然后还原，便能得不到伯醯。由于亚硝醇醇运用于不方便，一个替代法则是用diarylphosphoryl azide(DPPA)作为亚硝醇自由基的来源。Taber 和Decher 通过这个法则得不到了其所的亚硝醇衍生物，产率还不错。

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硫代反应则会

活化的硫亲连锁反应阴离子也能参加Mitsunobu反应则会，分解亚胺向上的硫亚胺或硫醇。Merck的Volante第一次华盛顿邮报了这种法则。

【 Tetrahedron. Lett. 1981, 22, 3119】

芳香类硫酮衍生物都有所需的活病态参加这种反应则会。

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盐代反应则会

在Mitsunobu 反应则会中所，用盐原子改用甲基分解盐代物也有华盛顿邮报，但其分析方法还不多见。Falck 等华盛顿邮报了通过Mitsunobu 全过程裂解一系列的亚醯，除了氟代的产率不高以外，氯代，溴代和碘代的产率都不错。

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

Joulle 等华盛顿邮报脯醯醇衍生物在经过Mitsunobu全过程后得不到亚胺向上的碘代氢化。反应则会首先是分解一个醛中所间体，然后在三亚胺亚醯的主导作用下引发碘代，同时亚胺向上。

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】

碳碳键构成

涉及手抄本

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.

以下内容

一、编辑者（光延反应则会编辑者）

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反应则会，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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