199534-14-0Relevant academic research and scientific papers
Oxygen-directed intramolecular hydroboration
Rarig, Robert-Andre F.,Scheideman, Matthew,Vedejs, Edwin
supporting information; body text, p. 9182 - 9183 (2009/02/03)
Metal-free homoallylic oxygen-directed intramolecular hydroboration is reported. Regioselectivities from 20:1 to 82:1 favoring the 1,3-dioxy-substituted products have been achieved using Me2S·BH3/TfOH followed by standard oxidative workup. Branching at the C5 position improves regioselectivity. Copyright
Regioselective nucleophilic ring opening of epoxides and aziridines derived from homoallylic alcohols
Tanner, David,Groth, Thomas
, p. 16139 - 16146 (2007/10/03)
The regioselectivity of nuclcopbilic ring opening of some 3,4-epoxy and 3,4-aziridino alcohols has been studied. The nucleophiles chosen were complex hydrides (LiAlH4, Red-Al and DIBAL) and Lipshutz- or Gilman-type organocuprate reagents. The C-4 substituent in the substrates was varied in order to study steric and electronic effects on the ring opening reactions. For alkyl substituents at C-4, most of the results can be explained on the basis of intramolecular delivery of the nucleophile to C-3 via a six-membered transition state, leading to 1,4-diols or 1,4-amine alcohol derivatives. In general, the epoxy alcohols gave poorer regioselectivity than the N-tosyl aziridino alcohols, for which selectivities of >95:5 were routinely obtained. The activating effect of a phenyl group at C-4 led to a switch in regiochemistry, with the 1,3-diol or 1,3-amino alcohol derivative as the major product.
