A TRANSITION-METAL-BASED METHOD FOR 1,2-DIAMINATION OF ALKENES - SYNTHESIS OF COBALT DINITROSOALKANES FROM ALKENES, NITRIC-OXIDE, AND (ETA-5-CYCLOPENTADIENYL)NITROSYLCOBALT DIMER AND THEIR REDUCTION TO PRIMARY VICINAL DIAMINES
A TRANSITION-METAL-BASED METHOD FOR 1,2-DIAMINATION OF ALKENES - SYNTHESIS OF COBALT DINITROSOALKANES FROM ALKENES, NITRIC-OXIDE, AND (ETA-5-CYCLOPENTADIENYL)NITROSYLCOBALT DIMER AND THEIR REDUCTION TO PRIMARY VICINAL DIAMINES
复制标题
DOI：
10.1021/om50001a001
复制
发表时间：
1983-01-01
期刊：
影响因子：
2.8
通讯作者：
BERGMAN, RG
中科院分区：
文献类型：
--
作者：
BECKER, PN;BERGMAN, RG
通式为R1 R2 C = CR 3R 4（R1（R2，R3，R4=烷基，氢）的未应变烯烃与[t）5-C5 H5 CoNO] 2/NO反应，以高产率产生通式为（5-C6 H6）（R1 R2 R3 R4 C2 N2 O2）Co的钴1，2-二亚硝基烷烃络合物。这些复合物中的许多都足够稳定，可以完全分离和表征;不太稳定的复合物可以成功地原位生成。最稳定的配合物是由四取代烯烃2，3-二甲基-2-丁烯衍生的。两种不同的钴二亚硝基烷烃络合物（5和6）分别由（E）-和（Z）-3-甲基-2-戊烯产生，确定反应立体特异性地发生。二亚硝基烷烃配体对CO和膦的置换是惰性的。这些络合物与LiAlH 4的还原在-78至-50 ℃下容易发生.总的来说，这构成了将烯烃转化为伯邻位脂族二胺的一般方法。还原的立体专一性取决于二亚硝基烷烃配体的取代基几何形状。由（E）-3-己烯衍生的络合物还原产生的主要非对映异构体是d，Z-3，4-己二胺。因此，主要的二胺是通过两个NH 2基团与烯烃的顺式加成形成的二胺。通过首先用（i '-Bu）2AlH还原其二亚硝基烷烃前体，然后用LiAlH 4还原，实现了d，Z-3，4-二氨基己烷生产的立体特异性增加2.5倍。
Unstrained alkenes of the general structure R1R2C= CR3R4 (R1 (R2, R3, R4= alkyl, hydrogen) react with [t) 5-C5H5CoNO] 2/NO to produce cobalt 1, 2-dinitrosoalkane complexes having the general formula (5-C6H6)(R1R2R3R4C2N202) Co in high yield. Many of these complexes are stable enough to isolate and characterize fully; less stable complexes can be generated successfully in situ. The most stable complex was derived from the tetrasubstituted alkene 2, 3-dimethyl-2-butene. Two different cobalt dinitrosoalkane complexes (5 and 6) result from (£)-and (Z)-3-methyl-2-pentene, respectively, establishing that the reaction occurs stereospecifically. The dinitrosoalkane ligands are inert to displacement by CO and phosphines. Reduction of these complexes with LiAlH4 occurs readily at-78 to-50 C. Overall, this constitutes a general method for conversion of alkenes into primary vicinal aliphatic diamines. The stereospecificity of reduction depends on the substituent geometry of the dinitrosoalkane ligand. The major diastereomer produced by reduction of the complex derived from (E)-3-hexene was d, Z-3, 4-diaminohexane. Thus, the major diamine is the one formed via syn addition of two NH2 groups to the alkene. An increase in stereospecificity by a factor of 2.5 for the production of d, Z-3, 4-diaminohexane was realized by first reducing its dinitrosoalkane precursor with (i'-Bu) 2A1H followed by LiAlH4.