title: Regio- and Stereoselective Homologation of 1,2-Bis(Boronic Esters): Stereocontrolled Synthesis of 1,3-Diols and Sch 725674.
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.
authors: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
authors: Alexander
authors: A
authors: Fawcett
authors: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
authors: Dominik
authors: D
authors: Nitsch
authors: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.|Department of Chemistry, COMSATS Institute of Information Technology, University Road, Abbottabad-, 22060, KPK, Pakistan.
authors: Muhammad
authors: M
authors: Ali
authors: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
authors: Joseph M
authors: JM
authors: Bateman
authors: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
authors: Eddie L
authors: EL
authors: Myers
authors: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
authors: Varinder K
authors: 0000-0003-0344-6430
authors: VK
authors: Aggarwal
keywords: 1,3-diols; Sch 725674; diboration; homologation; lithiation