181312-41-4Relevant academic research and scientific papers
A stereoselective, Sm(ii)-mediated approach to decorated cis-hydrindanes: Synthetic studies on faurinone and pleuromutilin
Findley, Thomas J. K.,Sucunza, David,Miller, Laura C.,Helm, Matthew D.,Helliwell, Madeleine,Davies, David T.,Procter, David J.
, p. 2433 - 2451 (2011)
The cis-hydrindane motif is found in a number of natural products that display important biological activity. A flexible, stereoselective approach to the framework has been developed that features highly diastereoselective, SmI2-mediated cyclisations. The strategy has been exploited in the first synthesis of the proposed structure of faurinone and an approach to the skeleton of the antibacterial natural product, pleuromutilin.
Synthesis of oxaspirannic building blocks by regioselective Nitroso-Diels-Alder reactions
Sancibrao, Pierre,Gori, Didier,Kouklovsky, Cyrille,Vincent, Guillaume
supporting information, p. 5557 - 5560 (2013/06/26)
Spirocyclic structures: Nitroso-Diels-Alder reactions of 1,3-disubstituted cyclohexadienes were found to be regiodivergent, depending on the nitroso derivative used. Cycloaddition with Wightman's chloronitroso derivative was totally regio- and stereoselec
A flexible, stereoselective approach to the decorated cis-hydrindane skeleton: Synthesis of the proposed structure of faurinone
Findley, Thomas J. K.,Sucunza, David,Miller, Laura C.,Davies, David T.,Procter, David J.
supporting information; experimental part, p. 6862 - 6865 (2009/07/18)
A flexible, stereoselective approach to the cis-hydrindane motif found in a number of biologically active natural products that utilizes highly diastereoselective SmI2-mediated cyclizations of aldehyde and halide substrates was demonstrated. Aldehydes were prepared to investigate the stereoselectivity of the proposed SmI2-mediated construction of the cis-hydrindane system. Treatment of aldehydes with SmI2 in THF and tBuOH resulted in successful cyclization and construction of three contiguous stereocenters. This cyclization proceeds through reduction of the aldehyde and addition of the resulting ketyl-radical anion to the alkene through anti-transition structure to give samarium (III) enolates. It was observed that SmI2-mediated halide-alkene cyclizations provide an easy alternative for the synthesis of less oxygenated targets.
Reactions of tin(IV) enolates obtained from O-stannyl ketyls under neutral free radical conditions
Enholm, Eric J.,Whitley, Paul E.,Xie, Yongping
, p. 5384 - 5390 (2007/10/03)
Under mild and neutral free radical conditions, an α,β-unsaturated ketone reacted with tributyltin hydride to produce an intermediate resonance-stabilized allylic O-stannyl ketyl. Upon subsequent hydrogen atom abstraction, a tin(IV) enolate was afforded which could be quenched with a variety of electrophiles and form new carbon-carbon bonds. Aldehydes react to produce aldol-type products and both intramolecular and intermolecular carbonyl addition reactions were investigated using this strategy. Using similar methodology, the tin(IV) enolate could be quenched in the presence of HMPA with various alkyl halides and α,β-unsaturated carbonyl compounds (Michael acceptors) to yield alkylated products in good yields. These reactions represent a very mild regioselective alternative to metal enolate formation which usually requires strong bases such as LDA or strongly reductive dissolving metal conditions to achieve success. New carbon skeletons for natural product synthesis can be readily constructed using this chemically neutral approach.
