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

提出了以N-氯代丁二酰亚胺和氯化亚锡(II)为原料，以醛和对甲苯磺胺为原料合成N-对甲苯磺酰亚胺的新方法，并将其应用于胺类化合物的亲核加成反应中。烯丙基三甲基硅烷加成高烯丙基胺(亚胺-烯丙化)：通过使用脂肪醛、α、β不饱和醛、含给电子或吸电子基团的芳香醛以及二氯甲烷中5×10*的酮，以高产率得到各种高烯丙基胺。2-丁烯基三甲基硅烷的非对映选择性亚胺-烯丙化反应：2-丁烯基三甲基硅烷与2-丁烯基三甲基硅烷反应，区域选择性地生成抗1-取代的2-甲基-3-烯基胺(=100%伽马)，非对映选择性地生成抗1-取代的2-甲基-3-烯基胺(&gt；90%)。乙酸异丙烯的亚胺-丙酮化反应：乙酸异丙烯在与上述烯丙化反应相同的条件下，使N-对甲苯磺酰亚胺发生丙酮化反应，生成1-(N-对甲苯基氨基)丁烷-3-酮。格氏试剂反应：在回流的TI-IF中生成N-对甲苯磺酰亚胺，然后加入5等摩尔量的苯基溴化镁，以50%的产率生成N-对甲苯磺酰二苯基甲胺。烯丙基、乙烯基和烷基卤化镁也与N-对甲苯磺酰亚胺反应生成相应的胺。由于亚胺质子的提取和与二氯代氧化锡的反应消耗，该方法需要过量的格氏试剂。因此，用碱处理N-对甲苯磺胺，然后用乙醚提取得到的溶液，将格氏试剂的数量从5等摩尔量减少到1.5等摩尔量。2-丁烯基氯化镁的合成-非对映选择性亚胺-烯丙基化：与2-丁烯基三甲基硅烷的加入相反，在碱处理后加入2-丁烯基氯化镁，然后用乙醚提取，导致合成非对映选择性。

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.