Asymmetric Catalysis with Silicon‐Based Cuprates: Enantio‐ and Regioselective Allylic Substitution of Linear Precursors. Issue 25 (12th May 2015)

• Record Type: Journal Article
• Authors: Hensel, Alexander; Oestreich, Martin
• Is Part Of: Chemistry. Volume 21:Issue 25(2015)
• Page Start: 9062
• Page End: 9065
• Publication Date: 2015-05-12
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201501371
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>An enantio‐ and regioselective allylic silylation of linear allylic phosphates that makes use of catalytically generated cuprate‐type silicon nucleophiles is reported. The method relies on soft bis(triorganosilyl) zincs as silicon pronucleophiles that are prepared in situ from the corresponding hard lithium reagents by transmetalation with ZnCl₂. With a preformed chiral N‐heterocyclic carbene–copper(I) complex as catalyst, exceedingly high enantiomeric excesses are achieved. The new method is superior to existing ones using a silicon–boron reagent as the source of the silicon nucleophile.</p> </abstract>