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Synthesis 2022; 54(08): 2049-2056
DOI: 10.1055/a-1701-7500
paper

Enantioselective, Copper-Catalyzed Addition of Nucleophilic Silicon to Alkenyl-Substituted Phosphine Oxides

Dou Hong 
,
Wenbin Mao 
,
Elisabeth Irran 
,
Martin Oestreich  ∗
W. M. thanks the China Scholarship Council for a predoctoral fellowship (2017–2021), and M.O. is indebted to the Einstein Foundation Berlin for an endowed professorship.
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Abstract

An enantioselective β-silylation of α,β-unsaturated phosphine oxide derivatives using a silylboronic ester as the silicon pronucleophile is reported. The reaction is catalyzed by copper salts in the presence of chiral pyridine–oxazoline (PyOx) ligands. Good to high enantioselectivities (≤95% ee) are obtained for β-aryl-substituted acceptors whereas alkyl residues in the β-position led to a lower ee value for 1° and no reaction for 2° and 3°. The new method represents another way of accessing α-chiral silanes and complements the known β-borylation.

Key words

asymmetric catalysis - conjugate addition - copper - phosphorus - silicon - silylation

Supporting Information



Publication History

Received: 02 November 2021

Accepted: 19 November 2021

Accepted Manuscript online:
19 November 2021

Article published online:
20 January 2022

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
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