20474-47-9Relevant academic research and scientific papers
Synthesis of (+)-discodermolide by catalytic stereoselective borylation reactions
Yu, Zhiyong,Ely, Robert J.,Morken, James P.
supporting information, p. 9632 - 9636 (2014/10/15)
The marine natural product (+)-discodermolide was first isolated in 1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides an inspiration for new reaction development. A new synthesis of discodermolide employs a previously undisclosed stereoselective catalytic diene hydroboration and also establishes a strategy for the alkylation of chiral enolates. Furthermore, this synthesis of discodermolide provides the first examples of the asymmetric 1,4-diboration of dienes and borylative diene-aldehyde couplings in complex-molecule synthesis. Borylation-based synthesis: The development of a strategy for stereocontrol in catalytic diene hydroboration enables the synthesis of a critical building block for the assembly of (+)-discodermolide. Combined with asymmetric catalytic diboration, hydroformylation, and borylative aldehyde-diene coupling reactions, (+)-discodermolide could then be prepared from simple hydrocarbon-based building blocks.
Regioselective α-alkylation of ketones with alkyl chlorides and fluorides via highly nucleophilic magnesium enamides
Hatakeyama, Takuji,Ito, Shingo,Yamane, Hiroaki,Nakamura, Masaharu,Nakamura, Eiichi
, p. 8440 - 8448 (2008/02/08)
A magnesium enamide derived from N-2-(N′,N′-dimethylamino)ethyl imine reacts with primary and secondary alkyl chlorides and fluorides to give an α-alkylated ketone in good to excellent yields upon hydrolysis of the imine moiety. Reactions of the highly nucleophilic magnesium enamide derived from an unsymmetrical ketone take place regioselectively. In addition, the C-C bond formation is stereospecific: a substantial inversion of stereochemistry at the electrophilic carbon center (Walden inversion) was observed, proving its potential utility for the production of optically active compounds.
Selective homologation of ketones and aldehydes with diazoalkanes promoted by organoaluminum reagents
Maruoka,Concepcion,Yamamoto
, p. 1283 - 1290 (2007/10/02)
Organoaluminum-promoted single homologation or ring expansion of ketones and aldehydes with diazoalkanes has been described, and among various organoaluminium reagents, exceptionally bulky methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD) is found to be highly effective for the selective homologation of various ketones and aldehydes.
