1394171-14-2Relevant articles and documents
Stereocontrolled synthesis of adjacent acyclic quaternary-tertiary motifs: Application to a concise total synthesis of (-)-filiformin
Blair, Daniel J.,Fletcher, Catherine J.,Wheelhouse, Katherine M. P.,Aggarwal, Varinder K.
, p. 5552 - 5555 (2014/06/10)
Lithiation/borylation methodology has been developed for the synthesis of acyclic quaternary-tertiary motifs with full control of relative and absolute stereochemistry, thus leading to all four possible isomers of a stereodiad. A novel intramolecular Zweifel-type olefination enabled acyclic stereocontrol to be transformed into cyclic stereocontrol. These key steps have been applied to the shortest enantioselective synthesis of (-)-filiformin to date (9 steps) with full stereocontrol. True to (fili)form: Lithiation/borylation methodology has been developed for the synthesis of acyclic quaternary-tertiary motifs with full control of relative and absolute stereochemistry, thus leading to all four possible isomers of a stereodiad. A novel intramolecular Zweifel-type olefination enabled acyclic stereocontrol to be transformed into cyclic stereocontrol. These key steps were applied to the enantioselective synthesis of (-)-filiformin.
The total synthesis of (-)-aplysin via a lithiation-borylation- propenylation sequence
Fletcher, Catherine J.,Blair, Daniel J.,Wheelhouse, Katherine M.P.,Aggarwal, Varinder K.
, p. 7598 - 7604 (2012/09/21)
A concise, highly enantioselective synthesis of sesquiterpene natural products (-)-debromoaplysin and (-)-aplysin has been completed. The key steps included lithiation-borylation of a secondary benzylic carbamate to give a tertiary boronic ester followed by propenylation which installed the quaternary stereocenter with complete enantioselectivity. Subsequent RCM followed by deprotection and in situ cyclization led to debromoaplysin with good diastereoselectivity from which the target compound was prepared in just eight overall steps.
