Regio‐ and Stereoselective Homologation of 1,2‐Bis(Boronic Esters): Stereocontrolled Synthesis of 1,3‐Diols and Sch 725674 |
| |
| Authors: | Alexander Fawcett Dr Dominik Nitsch Prof Dr Muhammad Ali Joseph M Bateman Dr Eddie L Myers Prof Dr Varinder K Aggarwal |
| |
| Institution: | 1. School of Chemistry, University of Bristol, Bristol, UK;2. Department of Chemistry, COMSATS Institute of Information Technology, Abbottabad-, Pakistan |
| |
| Abstract: | 1,2‐Bis(boronic esters), derived from the enantioselective diboration of terminal alkenes, can be selectively homologated at the primary boronic ester by using enantioenriched primary/secondary lithiated carbamates or benzoates to give 1,3‐bis(boronic esters), which can be subsequently oxidized to the corresponding secondary‐secondary and secondary‐tertiary 1,3‐diols with full stereocontrol. The transformation was applied to a concise total synthesis of the 14‐membered macrolactone, Sch 725674. The nine‐step synthetic route also features a novel desymmetrizing enantioselective diboration of a divinyl carbinol derivative and high‐yielding late‐stage cross‐metathesis and Yamaguchi macrolactonization reactions. |
| |
| Keywords: | 1 3-diols diboration homologation lithiation Sch 725674 |
|
|
