Asymmetric catalysis via dynamic substrate/ligand/rare earth metal conglomerate.

Asymmetric catalysis via dynamic substrate/ligand/rare earth metal conglomerate.
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DOI:
10.1021/ja800326d
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发表时间:
2008-04
影响因子:
15
通讯作者:
Akihiro Nojiri;N. Kumagai;M. Shibasaki
Akihiro Nojiri;N. Kumagai;M. Shibasaki
中科院分区:
化学1区
文献类型:
--
作者:
Akihiro Nojiri;N. Kumagai;M. Shibasaki

文献摘要

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描述了一种酰胺配体/Sc(OiPr)3催化剂促进的α-氰基酮和N-叔丁氧羰基亚胺的高对映体和非对映体选择性催化不对称Mannich型反应。在有/没有催化剂预络合的情况下获得了类似的反应结果,这表明非有序聚集体混合物中的反应组分在反应过程中协调形成有序的过渡态。光谱数据和Eyring图与这一假设是一致的。
A highly enantio- and diastereoselective catalytic asymmetric Mannich-type reaction of alpha-cyanoketones and N-Boc imines promoted by an amide ligand/Sc(OiPr)3 catalyst is described. The similar reaction outcome is obtained with/without precomplexation of catalyst, suggesting that reaction components in a non-ordered conglomerate mixture orchestrate to form an ordered transition state during the reaction. Spectroscopic data and Eyring plot are consistent with this assumption.