ALIPHATIC AMINES OF PHARMACOLOGIC INTEREST. I. 2-AMINO ALKANOLS AND THEIR DERIVATIVES²

The photochemical nucleophile–olefin combination, aromatic substitution (photo-NOCAS) reaction. Part 10: intramolecular reactions involving alk-4-enols and 1,4-dicyanobenzene

“…The residue was distilled at atmospheric pressure to yield 4.6 g (67%) of the alcohol 17 (bp 156-157°C). The I H nrnr spectrum was similar to that reported in the literature (22,29). 'H nrnr (250.13 MHz, CDCl,) ST,,: 1.20 (d, 3H, ,J,, = 6.1 HZ, CH, (1-H) (5) (1.2 g, 0.0078 mol), in 80 mL of acetonitrile was degassed with nitrogen and irradiated for 139 h using a 1-kW lamp.…”

Asymmetric Synthesis of Highly Substituted β-Nitro Alcohols and Enantiomerically Enriched 4,4,5-Trisubstituted Oxazolidinones

“…Finally, in view of the importance of oxazolidinones in both asymmetric synthesis and medicinal chemistry we briefly investigated reduction of the nitro alcohols to the corresponding amino alcohols followed by phosgenation to give the heterocycle. Nitro alcohols have been reduced to amino alcohols under a variety of conditions although the yields are often very modest. − In our hands similarly disappointing yields were obtained by most methods. Eventually, it was found that hydrogenation with Raney nickel afforded amino alcohols in modest yield accompanied by considerable retro-Henry product which, it was reasoned, arose from the basic nature of the Raney nickel.…”