Rhenium-catalyzed diastereoselective synthesis of aminoindanes via the insertion of allenes into a C-H bond

Organic Letters

Volumn 12, Issue 19, 2010, Pages 4274-4276

  Kuninobu, Yoichiro ^a   Yu, Peng ^a   Takai, Kazuhiko ^a  

^a OKAYAMA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 77957102792     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol101627x     Document Type: Article

References (43)

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23. We have already reported several rhenium-catalyzed transformations via C-H bond activation. See
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32. 10, previously revealed to have catalytic activities in promoting transformations via C-H bond activation, did not give any products via the insertion of allene 2a into the C-H bond of ketimine 1a.
33. Another group has also reported rhenium-catalyzed transformation via C-H bond activation. See: Chen, H. Y.; Hartwig, J. F. Angew. Chem., Int. Ed. 1999, 38, 3391
34. 3.
35. n: 1.0 mol %, 9%; 2.5 mol %, 72%; 10 mol %, 45%.
36. 3CN, 23%.
37. Investigation of reaction time: 1 h, 10%; 3 h, 53%; 8 h, 68%; 24 h, 72%.
38. The stereochemistry of 3a was determined by differential nuclear Overhauser effect (difNOE) measurements. See the following structure
39. During our investigations, one example of iridium-catalyzed insertion of an allene into an aromatic C-H bond was reported. See: Zhang, Y. J.; Skucas, E.; Krische, M. J. Org. Lett. 2009, 11, 4248
40. However, the reaction point is quite different from our reaction. The reaction occurs at the terminal position (α-position) of an allene, whereas our reaction proceeded at the β-position of the allene.
41. When 1-methyl-2-phenyl-1 H -imidazole or 2-phenylpyridine was employed as a substrate, allene 2a inserted into a C-H bond at the ortho -position of the aromatic substrates and alkenylated products was obtained in low yields (ca. 20%).
42. We assume two possible pathways to explain the mechanism for the formation of bicyclic compound 8. One possibility is that after the insertion of allene 2a into a C-H bond of ketimine 7, intramolecular nucleophilic cyclization did not occur, and instead, reductive elimination followed by electrocyclic reaction and isomerization of the olefin moieties proceeded. The other is that intermolecular aza-Diels-Alder reaction between allene 2a and ketimine 7 and isomerization of the olefin occurred sequentially.
43. In the case of using an allene with a chlorine, bromine, or iodine atom (6-halo-1,2-hexadienes), the desired aminoindanes were formed in trace amounts.