312298-83-2Relevant academic research and scientific papers
Diastereoselective Three-Component 3,4-Amino Oxygenation of 1,3-Dienes Catalyzed by a Cationic Heptamethylindenyl Rhodium(III) Complex
Burg, Finn,Rovis, Tomislav
supporting information, p. 17964 - 17969 (2021/11/10)
The direct oxyamination of olefins is a compelling tool to rapidly access β-amino alcohols-a privileged motif ubiquitous in natural products, pharmaceuticals and agrochemicals. Although a variety of expedient methods are established for simple alkenes, selective amino oxygenation of 1,3-dienes is less explored. Within this context, methods for the oxyamination of 1,3-dienes that are selective for the internal position remain unprecedented. We herein report a modular three-component approach to perform an internal and highly diastereoselective amino oxygenation of 1,3-dienes catalyzed by a cationic heptamethylindenyl (Ind*) Rh(III) complex.
Intramolecular Diels-Alder reactions of 1-phenylsulfonylalka-1,2,(ω - 3),(ω - 1)-tetraenes
Bull, James R.,Gordon, Richard,Hunter, Roger
, p. 3129 - 3139 (2007/10/03)
Methods are described for conversion of a series of (E)-alka-(ω - 3),(ω - 1)-dienals 2, via ethynylation to the corresponding alkadienynols 3, followed by sequential [2,3] sigmatropic rearrangement of their derived phenylsulfenate esters and chemoselective oxidation, into 1-phenylsulfonylalka-1,2,(ω - 3),(ω - 1)-tetraenes 5, which are used to study the influence of tether length and peripheral substitution upon intramolecular cycloaddition reactivity and selectivity. It is demonstrated that (6E)-1-phenylsulfonylnona-1,2,6,8-tetraene 5c and substrates featuring an analogous ethylene linkage between the functional termini, display exceptionally high intramolecular Diels-Alder (IMDA) reactivity, accompanied by exo-diastereoselectivity. Comparative studies are described, which delineate structure-reactivity trends and demonstrate the unique capacity of the dienophilic allenyl terminus to impose reactivity-enhancing conformational constraints upon IMDA processes in favourable cases. Preliminary investigations into substrates incorporating cyclic dienyl substructures are reported, and a novel approach to spiro[4.5]decanoid ring systems is described. The Royal Society of Chemistry 2000.
