Catalytic asymmetric [3,3]-rearrangements of allylic acetimidates
Catalytic asymmetric [3,3]-rearrangements of allylic acetimidates
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DOI：
10.1039/c4cy01749h
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发表时间：
2015-01-01
影响因子：
5
通讯作者：
Peters, Rene
中科院分区：
文献类型：
--
作者：
Bauer, J. Moritz;Peters, Rene
对映体纯的烯丙基胺作为先进的和有价值的合成结构单元的流线型合成途径对于药物科学是重要的。烯丙基三卤代乙酰亚胺酯的重排反应是制备具有高对映体选择性和区域选择性的支化手性烯丙基三卤代乙酰胺的一种有吸引力的方法。在本文中，我们报告了我们的研究相应的非卤代乙酰亚胺酯，这可能会提供经济优势，避免CX 3基团的催化不对称重排。区域选择性标题反应以高水平的对映体选择性进行，提供高产率并且仅需要低催化剂负载。此外，产生的N-乙酰基和N-苯乙酰基官能团提供了随后温和的酶促酰胺水解的选择，以获得几乎对映体纯的烯丙基胺。
A streamlined synthetic access to enantiomerically pure allylic amines as advanced and valuable synthetic building blocks is important for pharmaceutical sciences. The rearrangement of allylic trihaloacetimidates is known as an attractive method to furnish branched chiral allylic trihaloacetamides with high levels of enantio- and regioselectivity. In the present article we report our studies on the catalytic asymmetric rearrangement of the corresponding non-halogenated acetimidates, which might provide economic advantages by avoiding CX3 groups. The regioselective title reaction proceeds with high levels of enantio-selectivity, provides high yields and requires only low catalyst loadings. In addition, the generated N-acetyl and N-phenacetyl functionalities offer the option of a subsequent mild enzymatic amide hydrolysis to get access to nearly enantiopure allylic amines.