Development of method for preparing N-tosyliminiums and its application into synthesis of homoallylic amines

N-甲苯磺酰亚胺的制备方法开发及其在高烯丙胺合成中的应用

• 批准号: 09640710
• 负责人: MASUYAMA Yoshiro
• 金额: $ 2.11万
• 依托单位: Sophia University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640710/
• 关键词: imine-allylation; homoallylamines; N-tosyliminiums; tin (II) chloride; N-chlorosuccinimide; imine-acetonylation; diastereoselectivity; regioselectivity; アリルトリメチルシラン

Novel method for preparing N-tosyliminiums from aldehydes and tosylamide with N-chiorosuccinimide and tin(II) chloride was developed and was applied into synthesis of amine derivatives via addition of nucleophiles to the iminiums.1. Synthesis of homoallylic amines by addition of allyltrimethylsilane (imine-allylation) : Various homoallylic amines were obtained in high yields by the use of aliphatic aldehydes, alpha, beta-unsaturated aldehydes, aromatic aldehydes bearing electron-donating or electron-withdrawing groups, and ketones at 5*10* in dichioromethane.2. Diastereoselective imine-allylation by 2-butenyltrimethylsilane : Addition of 2- butenyltrimethylsilane produced anti 1-substituted 2-methylbut-3-enylamines regioselectively (=100% gamma) and diastereoselectively (>90% anti).3. Imine-acetonylation by isopropenyl acetate : Isopropenyl acetate caused acetonylation of N- tosyliminiums under the same conditions as those of allylation described above to produce 1-(N-tosylamino)butan-3 -ones.4. Reaction of Grignard reagents : Formation of N-tosyliminiums in refluxing TI-IF followed by addition of 5 equimolar amounts of phenylmagnesium bromide produced N-tosyldiphenylmethylamine in 50% yield. Allyl, vinyl, and alkylmagnesium halides also reacted with N-tosyliminiums to afford the corresponding amines. Consumed by the abstraction of iminium proton and the reaction with dichiorotin oxide, excess Grignard reagents needed in this method. Thus, the treatment of N-tosyliminiums with bases followed by the extraction of the resulting solution with ether reduced the quantity of Grignard reagents from 5 to 1.5 equimolar amounts.5. syn-Diastereoselective imine-allylation by 2-butenylmagnesium chloride : Addition of 2-butenylmagnesium chloride after the treatment with bases followed by the extraction with ether led to syn-diastereoselection, in contrast to the addition of 2-butenyltrimethylsilane.

建立了由醛和甲苯磺酰胺与N-氯代琥珀酰亚胺和氯化锡(II)制备N-甲苯磺酰亚胺的新方法，并将其应用于通过亲核试剂与亚胺加成合成胺衍生物。 1．通过烯丙基三甲基硅烷加成合成高烯丙胺（亚胺烯丙基化）：通过使用脂肪醛、α、β-不饱和醛、带有给电子或吸电子基团的芳香醛和酮，以高产率获得各种高烯丙胺5*10* 在二氯甲烷中。2. 2-丁烯基三甲基硅烷的非对映选择性亚胺烯丙基化：添加2-丁烯基三甲基硅烷可区域选择性地（=100%γ）和非对映选择性地（>90%抗）产生反1-取代的2-甲基丁-3-烯基胺。3．乙酸异丙烯酯的亚胺乙酰化：乙酸异丙烯酯在与上述烯丙基化相同的条件下引起N-甲苯磺酰亚胺的乙酰化，产生1-(N-甲苯磺酰氨基)丁-3-酮。4．格氏试剂的反应：在回流的 TI-IF 中形成 N-甲苯磺酰亚胺，然后添加 5 等摩尔量的苯基溴化镁，产生 N-甲苯磺酰基二苯基甲胺，产率 50%。烯丙基、乙烯基和烷基卤化镁也与N-甲苯磺酰亚胺反应，得到相应的胺。该方法需要过量的格氏试剂，由于亚胺质子的提取以及与氧化二氯锡的反应而被消耗。因此，用碱处理N-甲苯磺酰亚胺，然后用乙醚萃取所得溶液，将格氏试剂的量从5等摩尔量减少到1.5等摩尔量。5． 2-丁烯基氯化镁的顺式非对映选择性亚胺烯丙基化：与添加2-丁烯基三甲基硅烷相反，在用碱处理后添加2-丁烯基氯化镁，然后用乙醚萃取，导致顺式非对映选择。