Iterative Stereospecific Reagent-Controlled Homologation of Pinacol Boronates by Enantioenriched α-Chloroalkyllithium Reagents

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Abstract

Reaction of pinacol boronates with putative enantioenriched α-chloroalkyllithium species, generated in situ from homochiral α-chloroalkylsulfoxides by sulfoxide ligand exchange with t-BuLi in PhMe at −78 °C, gave chain-extended boronic ester products with generally excellent stereochemical fidelity. Iteration of this stereospecific reagent-controlled homologation (StReCH) process enabled the programmed synthesis of all four stereoisomers of a stereodiad-containing model system (4-benzyl-1,6-diphenylhexan-2-ol) with er ≥ 97:3 in all cases.

Citing Articles

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This article has been cited by 5 ACS Journal articles (5 most recent appear below).

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  Stereocontrolled Generation of α-Metalated S,O-Acetals by Sulfoxide-Ligand Exchange from Cyclic Dithioorthoformate Monooxides

  Adam L. Barsamian and Paul R. Blakemore
  Organometallics2012 31 (1), 19-22

  • Stereocontrolled Generation of α-Metalated S,O-Acetals by Sulfoxide-Ligand Exchange from Cyclic Dithioorthoformate Monooxides

    Adam L. Barsamian and Paul R. Blakemore
    Organometallics2012 31 (1), 19-22

    Treatment of trans or cis 2-isopentoxy-1,3-benzodithiolane-S-oxides with EtMgCl gave configurationally stable (≥2.5 h, at −78 °C) stereodefined α-magnesiated S,O-acetals that incorporated D atoms in a stereospecific manner upon reaction with CD3OD. α-...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Iterative Stereospecific Reagent-Controlled Homologation Using a Functionalized α-Chloroalkyllithium: Synthesis of Cyclic Targets Related to Epibatidine

  Christopher R. Emerson, Lev N. Zakharov, and Paul R. Blakemore
  Organic Letters2011 13 (6), 1318-1321

  • Iterative Stereospecific Reagent-Controlled Homologation Using a Functionalized α-Chloroalkyllithium: Synthesis of Cyclic Targets Related to Epibatidine

    Christopher R. Emerson, Lev N. Zakharov, and Paul R. Blakemore
    Organic Letters2011 13 (6), 1318-1321

    Enantioenriched 1-chloro-2-(1,3-dioxolan-2-yl)ethyllithium was generated by PhLi initiated sulfoxide-ligand exchange and deployed in situ for sequential double stereospecific reagent-controlled homologation (StReCH) of B-(2-chloro-pyrid-5-yl) pinacol ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Homologation of Boronic Esters with Lithiated Epoxides for the Stereocontrolled Synthesis of 1,2- and 1,3-Diols and 1,2,4-Triols

  Emeline Vedrenne, Olov A. Wallner, Maxime Vitale, Frank Schmidt and Varinder K. Aggarwal
  Organic Letters2009 11 (1), 165-168

  • Homologation of Boronic Esters with Lithiated Epoxides for the Stereocontrolled Synthesis of 1,2- and 1,3-Diols and 1,2,4-Triols

    Emeline Vedrenne, Olov A. Wallner, Maxime Vitale, Frank Schmidt and Varinder K. Aggarwal
    Organic Letters2009 11 (1), 165-168

    Lithiated epoxides react stereospecifically with boronic esters to give syn-1,2-diols, a process that can be used iteratively to create triols containing four stereogenic centers.

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Mild Synthesis of Organophosphorus Compounds:  Reaction of Phosphorus-Containing Carbenoids with Organoboranes

  Monika I. Antczak and Jean-Luc Montchamp
  Organic Letters2008 10 (5), 977-980

  • Mild Synthesis of Organophosphorus Compounds:  Reaction of Phosphorus-Containing Carbenoids with Organoboranes

    Monika I. Antczak and Jean-Luc Montchamp
    Organic Letters2008 10 (5), 977-980

    Organoboranes react with phosphorus-containing carbenoids to produce a variety of functionalized organophosphorus compounds under mild conditions. In some cases, selective migration of one group attached to boron can be observed. Phosphoniteborane ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Asymmetric Sulfur Ylide Reactions with Boranes:  Scope and Limitations, Mechanism and Understanding

  Guang Y. Fang, Olov A. Wallner, Nadia Di Blasio, Xavier Ginesta, Jeremy N. Harvey, and Varinder K. Aggarwal
  Journal of the American Chemical Society2007 129 (47), 14632-14639

  • Asymmetric Sulfur Ylide Reactions with Boranes:  Scope and Limitations, Mechanism and Understanding

    Guang Y. Fang, Olov A. Wallner, Nadia Di Blasio, Xavier Ginesta, Jeremy N. Harvey, and Varinder K. Aggarwal
    Journal of the American Chemical Society2007 129 (47), 14632-14639

    The reactions of aryl-stabilized sulfur ylides with organoboranes has been studied under a variety of conditions. At 5 or −78 °C, the reaction with Et3B gave a mixture of the first and second homologation products, but at −100 °C, only the first ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

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