DIAZADIENES AS CONTROLLING LIGANDS IN CATALYSIS .5. SYNTHESIS OF CHIRAL DIAZADIENES R]-N=CR'-CR'=N-R
DIAZADIENES AS CONTROLLING LIGANDS IN CATALYSIS .5. SYNTHESIS OF CHIRAL DIAZADIENES R]-N=CR'-CR'=N-R
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DOI：
10.1002/cber.19841170222
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发表时间：
1984-01-01
期刊：
影响因子：
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通讯作者：
DIETRICH, J
中科院分区：
文献类型：
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作者：
DIECK, HT;DIETRICH, J
乙二醛（作为水合物）或2，3-丁二酮与伯胺的缩合原则上是简单的反应。不幸的是，具有仲或叔α-碳的脂族胺通常产生不需要的加成产物。在特定的反应条件下，由（R-1-苯基-乙胺（1）和（1 S，2S，3S，5 R）-3-（氨甲基）蒎烷（2）得到所需的二亚胺（二氮二烯（dad）：R*- N = CR' - CR' = N-R *，R' = H，CH 3）4和6 - 8。根据二酮的不同，吗啉代吗啉9和双恶唑烷10由（S）-2-氨基-1-丁醇（3）形成，它们与富电子金属以其异构体dad形式结合（（dad）Mo（CO）411和12）。无环dad结构通过O-甲硅烷基化稳定（14，15）。（dad）铁（0）催化的丁二烯与这些控制配体的二聚为4-乙烯基-1-环己烯发生对映体过量高达16%。
The condensation of glyoxal (as hydrate) or 2,3‐butanedione with primary amines is, in principle, a simple reaction. Unfortunately, aliphatic amines with secondary or tertiary α‐carbons often give unwanted addition products. Under special reaction conditions the desired diimines (diazadienes (dad): R*– N = CR' – CR' = N – R*, R' = H, CH3)4, and6 – 8are obtained from (R‐1‐phenyl‐ethylamine (1) and (1S,2S,3S,5R)‐3‐(aminomethyl)pinane (2). Depending on the dione, a morpholinomorpholine9and a bioxazolidine10are formed from (S)‐2‐amino‐1‐butanol (3), which are bound by electron‐rich metals in their isomeric dad form ((dad)Mo(CO)411and12). The acyclic dad structure is stabilized byO‐silylation (14, 15). The (dad)iron(0) catalyzed dimerization of butadiene with these controlling ligands to 4‐vinyl‐1‐cyclohexene occurs with an enantiomeric excess up to 16%.