Anomalous Reductions of 7-Substituted Norbornadienes with Diimide

Abstract

second fraction (bp 134-136°) was better than 95% monchloride (3.2 g, 80%). It could be used as such for further reaction. On vpc examination (Silicone oil column 20 ft, or Ucon-550 column 6 ft, or diisodecyl phthalate column 6 ft) the material was found to consist of three monochlorides which were in the ratio 2.5:95.0:2.5. The major component was separated by chromatography, The minor components were not identified. The purified monochloride, «25d 1.4725, had strong infrared absorptions (µ, neat liquid) at 3.35, 7.78, 10.85, and 14.10; mol wt 116, 118 (mass spectrometry). (For the nmr spectrum, see Results.

Aerobic Reduction of Olefins by In Situ Generation of Diimide with Synthetic Flavin Catalysts

“…[36] In a typical reaction, selective 1,2-deuteriation of 2-exo,3-exo-bis(acetoxymethyl)bicyclo-A C H T U N G T R E N N U N G [2.2.1]hept-5-ene (8) can be performed with only 1.2 equiv of ND 2 ND 2 ·D 2 O to afford 9 in a yield of 93 % [Eq. (6)].…”

The preparation, properties and reactions of diimide

“…Relative rates of reaction with a large variety of unsaturated compounds have been reported [7,9,14,15,91,124,131,133,136,137,[141][142][143][144] from various laboratories. These data are semi-quantitative at best; some are based simply on yields of reduction products from single reagents under some standard conditions of diimide generation; others are derived from the competitive reduction of pairs of reagents.…”

The chemistry of aurodox and related antibiotics

“…Stereoselective hydrogenation with diimide involving hydrogen addition from the more hndered side has been demonstrated, inter alln, with 7-oxynorbornadienes via rxo-cis addition (51). To prepare the 9P-epimer 7% stereoselective hydrogen addition from the more kndered side was required.…”