Cu(I) catalyzed reaction of hydroxylamines

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BassanDavid_2015_11_19.pdf (3.89 MB)

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2015

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DOI:
http://dx.doi.org/10.22029/jlupub-10358

Abstract

In the presented dissertation the intramolecular Cu(I) catalyzed amino oxygenation of hydroxylamines was further investigated and optimized. It was determined that by inserting a p-NO2 group on the benzoyl rest of the O increased the reactivity of the hydroxylamine. Both the selectivity and general yield were improved, under different reaction conditions, kinetic or thermal. At RT with the activation through 1eq. BF3OEt after 6 hours, or in the MW at 75°C with 2 eq. BF3OEt after 10 minutes, the five ring is formed relatively selectivly. At 100°C after 1 hour in an oil bath, or 5 minutes in the MW without BF3OEt the selectivity reverses. The general applicability of this reaction was tested for benzylic, allylic and alkan N-substituted Hydroxylamines, as well as for the placement of carbon substituents along the carbon skeleton resulting in the ring. It was found that the formation of the 6-ring is highly dependent on the geminal dialkyl groups. It was also determined that varying the length of the carbon chain to form 3, 4 or 7 membered rings did not occur, even with the higher reactivity. Yields of the 5-ring ranged from 76 to 32%, for the 6-ring they ranged from 48 to 15%.

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