MBH加合物的合成与应用

不对称有机催化是有机化学的一个重要的研究领域，其催化的反应具有反
应条件较为温和、催化剂廉价易得、无金属残留等诸多优势，这些优势使得有
机不对称催化在近些年来得到了迅速地发展，并在有机化学反应中被广泛应用。
MBH 反应是直接生成叔碳原子或季碳原子的较少的有机人名反应之一，
MBH 加合物也是有机合成中常用的合成子。目前经典的MBH 加合物有两种，
分别以醛和靛红为底物经过MBH 反应衍生而来，而这两类经典的MBH 加合物
一般用做C1 合成子或C3 合成子参与反应，这些反应经过诸多研究报道后已经
形成了较为完整的体系。但是遗憾的是，关于被用做C4, C6 等其他合成子的新
型MBH 加合物的开发，以及MBH 加合物的其他催化模式等方面的研究却颇为
罕见，需要深入研究以拓宽MBH加合物的应用。故此，本文研究内容旨在开发
新型的MBH 加合物并探索其在有机化学反应中的应用，详情如下：
MBH 加合物的一锅法合成。由MBH 醇为底物，DABCO 为催化剂，通过
“一锅法”高效合成得到了苯并噁嗪，目标产物产率63-98%。 同时，将
DABCO 催化剂通过调整变为NaOH/TBAB，同样通过“一锅法”高效得到了二
氢喹啉，目标产物产率35-95%。
苯并噁嗪参与的不对称[4+2]环加成反应。以苯并噁嗪和缺电子化合物为底
物，奎尼丁为催化剂，高效地以苯并噁嗪为C4 合成子得到了手性四氢喹啉，目
标产物产率47-95%，对映选择性80-93%，非对应选择性＞20:1。
苯并噁嗪合成二氢喹啉。以苯并噁嗪和硫叶立德为底物，硫叶立德利用自
身的碱性催化苯并噁嗪开环重排，节约了催化剂的损耗，高效地得到了一系列
二氢喹啉化合物，目标产物产率55-95%。
 

Asymmetric organic catalysis is an important research field in organic chemistry. It has
many advantages, such as mild reaction conditions, cheap catalyst, no metal residue,
etc., which makes the rapid development of organic asymmetric catalysis in recent
years. It is also widely used in the organic chemical reactions.
The MBH reaction is one of the fewer organic human name reactions that directly form
tertiary carbon atoms or quaternary carbon atoms, and MBH adducts are also used in
organic synthesis. At present, there are two classic MBH adducts, respectively,
aldehydes and isatin as substrates derived from MBH reactions, and these two types of
classic MBH adducts are generally used as C1 synthons or C3 synths to participate in
the reaction, and these reactions have formed a relatively complete system after many
research reports. Unfortunately, research reports on novel MBH adducts, and novel
asymmetric catalytic modes of MBH adducts are rare, which is needed to broaden the
application of MBH adducts. Therefore, the research content of this thesis aims to
develop new MBH adducts and explore their application. Details are as follows:
One-pot synthesis of MBH adducts. Using MBH alcohol as substrate and
triethylenediamine as catalyst, benzoxazine was obtained by efficient synthesis by the
"one-pot method", and the target product yield was 63-98%. At the same time, the
DABCO catalyst was adjusted to NaOH/TBAB, and dihydroquinoline was also
efficiently obtained by the "one-pot method", with a target product yield of 35-95%.
Asymmetric [4+2] cycloaddition reaction involving benzoxazine. Chiral
tetrahydroquinoline was obtained by using benzoxazine and electron-deficient adducts
as substrates and quinidine as catalysts, with benzoxazine as C4 synthesizers efficiently
obtaining chiral tetrahydroquinoline, with a target product yield of 47-95%,
enantioselectivity of 80-93%, and non-corresponding selectivity >of 20:1.
Dihydroquinoline was synthesized from benzoxazine. Using benzoxazine and sulfur
ylide as substrates, sulfur ylide used its own basic catalytic benzoxazine ring
rearrangement, which saved the loss of catalyst and efficiently obtained a series of
dihydroquinoline compounds with a target product yield of 55-95%.
 

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