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新型对映体纯的烷基亚胺钼基配合物。作为手性烯烃复分解催化剂的合成、表征及活性

New Enantiomerically Pure Alkylimido Mo-Based Complexes. Synthesis, Characterization, and Activity as Chiral Olefin Metathesis Catalysts.

作者信息

Pilyugina Tatiana S, Schrock Richard R, Müller Peter, Hoveyda Amir H

机构信息

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139.

出版信息

Organometallics. 2007 Jan 20;26(4):831-837. doi: 10.1021/om061001o.

DOI:10.1021/om061001o
PMID:19079732
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC2600727/
Abstract

Molybdenum olefin metathesis catalysts that contain aliphatic 1-phenylcyclohexylimido (NPhCy) and 2-phenyl-2-adamantylimido (NPhAd) groups and (S)-Biphen or (R)-Trip)(THF) ligands (Biphen = 3,3'-di-tert-butyl-5,5',6,6'-tetramethyl-1,1'-biphenyl-2,2'-diolate; Trip = 3,3'-bis(2,4,6-triisopropylphenyl)-2,2'-binaphtholate) have been prepared. Their catalytic activity and enantioselectivity in desymmetrization reactions such as ring-closing metathesis of amines and lactams and ring-opening/cross-metathesis of substituted norborneols with styrene were compared to the results obtained with the only known alkylimido catalyst Mo(NAd)(CHCMe(2)Ph)[(S)-Biphen]. The activities and enantioselectivities provided by these new chiral complexes vary significantly, but in virtually all instances explored were not superior to the adamantylimido analogs.

摘要

已制备出含有脂肪族1-苯基环己基亚胺基（NPhCy）和2-苯基-2-金刚烷基亚胺基（NPhAd）基团以及（S）-联苯二酚或（R）-三异丙基联苯二酚（THF）配体（联苯二酚=3,3'-二叔丁基-5,5',6,6'-四甲基-1,1'-联苯-2,2'-二醇；三异丙基联苯二酚=3,3'-双（2,4,6-三异丙基苯基）-2,2'-联萘酚）的钼烯烃复分解催化剂。将它们在胺和内酰胺的闭环复分解以及取代降冰片醇与苯乙烯的开环/交叉复分解等去对称化反应中的催化活性和对映选择性与唯一已知的烷基亚胺基催化剂Mo（NAd）（CHCMe（2）Ph）[（S）-联苯二酚]所得到的结果进行了比较。这些新型手性配合物所提供的活性和对映选择性有很大差异，但在几乎所有探索的实例中都不优于金刚烷基亚胺类似物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/16e0/2600727/33e24d0b56ba/nihms61865f1.jpg

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