Enantioselective allylic alkylation of stereodefined polysubstituted copper enolates as an entry to acyclic quaternary carbon stereocentres† †Electronic supplementary information (ESI) available. CCDC 1488151. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc03036j Click here for additional data file. Click here for additional data file.

Table of Contents General methods S1 Reagents and materials S2 General protocol for the preparation of starting chiral ynamides S3 General procedures for the allylation of stereodefined trisubstituted copper enolate S5 Optimization reactions S8 Products of the enantioselective allylic alkylation reaction S9 Cleavage of oxazolidinone moiety 4 S19 References S21 X-Ray crystallographic analysis data of 4p S22 Analytical HPLC analysis data for the products of enantioselective allylic alkylation S36 NMR spectra S53 Electronic Supplementary Material (ESI) for Chemical Science.