Rearrangements alcohol synthesis

Allylic nitro compounds undergo [2.3]sigmatropic rearrangement to afford rearranged alcohols, as shown in Eq. 7.4346 and Eq. 7.44 47 Because the allylic nitro compounds used in these reactions are readily prepared either by the Henry reaction or the Michael addition, these reactions may be useful in organic synthesis. 

AUyl transfer reactions, 73, 1 Allylic alcohols, synthesis from epoxides, 29, 3 by Wittig rearrangement, 46, 2 Allylic and benzylic carbanions, heteroatom-substituted, 27, 1 Allylic hydroperoxides, in... 

Appropriate catalysts are necessary for all fuel and chemical synthesis. The basic concept of a catalytic reaction is that reactants adsorb onto the catalyst surface and rearrange and combine into products that desorb from the surface. One of the fundamental functional differences between various syngas synthesis catalysts is whether the adsorbed CO molecule dissociates on the catalyst surface. For FTS and higher alcohol synthesis, CO dissociation is a necessary reaction condition. For methanol... 

A three-stage synthesis of allylic alcohols has been devised (Scheme 32)," which consists of (i) alkylation of a sulfone-stabilized allylic carbanion (ii) peroxy acid oxidation of the allylic sulfone to give a 2,3-epoxy sulfone and (iii) reductive elimination of the 2,3-epoxy sulfone to give the allylic alcohol. The overall strategy is similar to that of the Evans-Mislow allylic alcohol synthesis based on the 2,3-sig-matropic rearrangement of allylic sulfoxides. However, there are regiochemical advantages to the sul-... 

Allylic sulfoxides are known to equilibrate with their isomeric sulfenates via a 2,3-sigmatropic shift, which has been developed into a useful allylic alcohol synthesis when the unstable sulfenate is trapped (Scheme 14). However, this rearrangement is reversible and so need not necessarily interfere with pyrolytic elimination of the sulfoxide, e.g. the long-chain hydroxydiene (69) was obtained on pyrolysis of the sulfoxide (68 equation 32). A study of substitution effects on the relative rates of rearrangement... 

Ohler, E.. and Zbiral. Ei.. Oxidative rearrangement of phosphorus containing tertiary allylic alcohols. Synthesis of (3-oxo-l-cycloalkenyl)phosphonates, -methylphosphonates, -methyldiphenylphosphine oxides and their epoxy derivatives. Synthesis, 357, 1991. 

---