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Mechanistic variations in ionic hydrogenation of unsaturated phosphine and amine boranes
Timothy S De Vries1, Supriyo Majumder, Angela M Sandelin
1Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA.
Abstract:
Internal hydride transfer occurs when tethered carbocations are generated from unsaturated phosphine or phosphinite boranes. 3-Methylenecyclohexyl-derived boranes 12 or 18 react with MsOH to give ionic hydrogenation products with high syn-selectivity. With unsaturated amine boranes, initial hydrogen evolution gives BH(2)(OMs) complexes, but IH occurs using excess MsOH in a slower second stage. A diastereoselective reaction occurs from 26b using camphorsulfonic acid (first stage) and MsOH (second stage), affording 33 (68% ee) after hydrolysis.
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