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

基本信息

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

项目摘要

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.

开发了从醛和甲酰胺中制备N-氯化二酰亚胺和TIN（II）氯化物（II）氯化物的新方法，并通过在iminiums.1中添加核粒子来合成胺衍生物的合成。1。通过添加烯丙基甲基硅烷（亚胺 - 盟式）合成同甲基胺的合成：通过使用α-醛，α-非饱和醛醛，苯甲酸醛，芳族醛，芳族醛，芳族醛，芳族醛和电子脱甲酸盐，以电子方式和电子销售* ket-draffing and Dravking and Draffing and Draff Draffing at Draffing at Draffing Wenting and Draffing Wenting and Draffing Wenting and Draffing Wenting and Draffing Andemants，从高收率获得了各种同甲基胺。二甲烷2。 2-苯基三甲基硅烷的映射亚胺 - 依赖：添加2-丁基三甲基硅烷的添加产生抗1-叠加的2-甲基But-3-烯基胺的区域选择性（= 100％Gamma）和映射（> 90％抗）。3。乙酸异丙烯基的亚丙丙酰化：乙酸异丙烯基在与上述烯丙基裂解的条件下引起n- tosylimins的乙酰丙酸，以产生1-（n-tosylamino）butan-3 -Ones.4。 Grignard试剂的反应：在回流TI-IF中形成N-甲基矿物，然后再添加5个等摩尔量的苯基镁溴化苯基溴化物以50％的收率产生N-甲基二甲基甲基胺。烯丙基，乙烯基和烷基镁卤化物也与N-甲基矿物质反应，以提供相应的胺。由亚米尼质子的抽象和与氧化二分化的反应所消耗的，在这种方法中需要过多的grignard试剂。因此，用碱基处理N-二苯二亚菌的处理，然后用乙醚提取所得溶液，将Grignard试剂的量从5降低至1.5 e摩尔量。5。通过2-丁基二苯基氯化物的合成肌选择性亚胺 - 氯化物：与碱基处理后，添加2-丁烯基氯二酰氯化物，然后用乙醚提取乙醚导致合成二甲状腺素选择，与添加2-苯基三甲基三乙烷相反。