Simple primary anilines as iminium catalysts for the epoxidation of α-substituted acroleins

Advanced Synthesis and Catalysis

Volumn 349, Issue 6, 2007, Pages 802-806

  Erkkilä, Anniina ^a   Pihko, Petri M ^a   Clarke, Melanie Rose ^a  

^a Department of Chemical Technology   (Finland)

Author keywords

Anilines; Epoxides; Iminium catalysis; Organocatalysis

Indexed keywords

EID: 34547202127     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200700048     Document Type: Article

References (37)

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24. Support for this model can be obtained by inspecting the X-ray crystal structures for range of iminium ions derived from anilines. A statistical study of these X-ray structures is not possible due to low number of examples, but the available data suggests that the iminium ions derived from parent aniline tend to favor conformations where the iminium ion is conjugated with the aromatic ring. ortho-Substituted anilines, on the other hand, tend to favor non-coplanar conformations, with the iminium ion twisted out of conjugation with the ring. See the Supporting Information for examples.
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35. [14b] for similar results.
36. Catalyst 1i·TFA promoted the Diels-Alder reaction between cyclopentadiene and ct-benzylacrolein in 100% conversion after > 3 h. See the Supporting Informationfor details. In addition, catalyst 1i·HCl promoted the Diels-Alder reaction between cyclopentadiene and cinnamaldehyde in acetonitrile in 64% conversion after 18 h.
37. In preliminary experiments, chiral anilines have afforded the epoxidation products in up to 50% ee. Details of these experiments, including optimization of the protocol, will be reported separately.