氨基化合物也可以作为Mitsunobu 反应中的亲核试剂，取代羟基，生成取代的氨基化合物。同样，参与反应的胺必须有足够的酸性（pKa<13），能被PPh3/DEAD体系夺去质子。酰胺，磺酰胺，亚胺和叠氮化合物都可以参与反应。Weinreb 用这种方法，在经过连续两次的Mitsunobu 反应后，合成了天然产物SarainA的主环.

     近年来，相继发展了一些用于Mitsunobu 氨基取代反应的试剂，这些试剂在取代后，再脱去保护基而得到各种氨基化合物。

    Hart和Campbell报导2-[(trimethylsilyl)ethyl]sulfonyl（TES）保护的Boc酰胺，在Mitsunobu 氨基取代后，可以去保护生成Boc 保护的胺或胺的盐酸盐.

    Fukuyama报导硝基苯磺酰胺类化合物在经过Mitsunobu氨基取代后，能方便地用苯硫酚脱去磺酰基，得到仲胺.

     Bach 和Kather 报导Fmoc 保护的磺酰胺在Mitsunobu 氨基取代后，能直接脱去Fmoc 而得到磺酰胺.

     酰胺也能作为Mitsunobu 氨基取代反应的底物。比如下面的分子内氨基取代，得到氮杂环化合物.

      一个从Gabriel 氨基合成衍生过来的合成伯胺的方法，在Mitsunobu 氨基取代中用邻苯二甲酰亚胺作为亲核试剂，然后肼解，便得到手性翻转的伯胺.

     另一个合成伯胺的方法是在Mitsunobu 反应中用叠氮取代羟基，然后还原，便能得到伯胺.

     由于叠氮酸使用不方便，一个替代方法是用diarylphosphoryl azide (DPPA)作为叠氮基团的来源。Taber 和Decher 通过这个方法得到了相应的叠氮化合物，产率还不错.

       Myers报导磺酰肼与α-羟基取代炔经过Mitsunobu氨基取代反应，生成的产物不稳定，马上分解为丙二烯化合物，这是一个制备丙二烯化合物的比较便捷的方法.

有文献报道游离胺也可分子内关环

    N-Boc p-toluenesulfonamide (88mg, 0.322 mmol) was dissolved in dry THF (3 mL) and PPh3 (168 mg, 0.645 mmol) was added. The solution was stirred under nitrogen and the alcohol (0.215 mmol) was added followed by DEAD (0.083 mL, 0.53 mmol). The mixture was stirred at room temperature for 3 h, concentrated in vacuo and the residue was purified by flash column chromatography (P: E 4: 1) to give the product (62%).

    The de-protection was carried out according to the usual procedure.

Mitsunobu 法利用DPPA 合成伯胺方法示例

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

     The de-protection and hydrogenation were routine operations.

                 Mitsunobu 法分子内关环合成相应的环状胺方法示例

     To a solution of substituted proline (33.6 g, 0.1 mol) and PPh3 (31.5 g, 0.12 mol) in THF (200 mL) was dropped a solution of DEAD (18.8 mL, 0.12 mmol) in dry THF (50 mL) at ice bath. The reaction mixture was allowed to warm to stirred 20oC for 2 h. The filtrate was evaporated and stirred with EA (100 mL), and the product was collected by filtration (20.66 g, 74%). The solvent was removed under reduced pressure and the crude oil was purified by column chromatograghy to afford the desired product (27.3 g, 86%).

Mitsunobu 法合成丙二烯方法示例

    An oven-dried, 500-mL, round-bottomed flask equipped with a large football-shaped Teflon-coated magnetic stirring bar is charged with 15.7 g (60.0 mmol) of triphenylphosphine under an argon atmosphere. The flask is sealed with a rubber septum containing a needle adapter to an argon-filled balloon, and 120 mL of THF is added via cannula. The solution is cooled in a −15°C bath, and 9.02 mL (57.5 mmol) of diethyl azodicarboxylate is added via syringe over 2 min, followed immediately by the addition of a solution of 8.52 g (50.0 mmol) of 3-(tert-butyldimethyl silyl)-2-propyn-1-ol in 18 mL of THF via cannula over 2 min. After an additional 5 min, a solution of 13.0 g (60.0 mmol) of o-nitrobenzenesulfonyl hydrazide in 65 mL of THF is added to the reaction mixture over 5 min via cannula. The resulting orange-red solution is stirred at −15°C for 45 min, after which time the cold mixture is allowed to warm to 23°C and is held at that temperature for 5 hr. During this time, the evolution of dinitrogen is observed. The reaction mixture is poured into a 2-L separatory funnel containing 400 mL of pentane, and the resulting mixture is washed with four 500-mL

portions of ice-cold water. The organic layer is dried over anhydrous sodium sulfate, filtered, and concentrated by rotary evaporation at 0°C. The residue is purified by flash chromatography using a short column of 230-400 mesh silica gel (60 g, packed dry and eluted with pentane. The fractions containing the product are concentrated by rotary evaporation at 0°C to afford 5.38-5.39 g (70%) of (tert-butyldimethylsilyl)allene as a colorless liquid.