Enantio‐ and Regioconvergent Nickel‐Catalyzed C(sp<sup>3</sup>)−C(sp<sup>3</sup>) Cross‐Coupling of Allylic Electrophiles Steered by a Silyl Group
Nektarios Kranidiotis‐Hisatomi, Hong Yi, Martin Oestreich
Abstract
Abstract A two‐step sequence for the enantio‐ and diastereoselective synthesis of exclusively alkyl‐substituted acyclic allylic systems with a stereocenter in the allylic position is reported. The asymmetric induction and the site selectivity are controlled in an enantio‐ and regioconvergent nickel‐catalyzed C(sp 3 )−C(sp 3 ) cross‐coupling of regioisomeric mixtures of racemic α‐/γ‐silylated allylic halides and primary alkylzinc reagents. The silyl group steers the allylic displacement towards the formation of the vinylsilane regioisomer, and the resulting C(sp 2 )−Si bond serves as a linchpin for the installation of various C(sp 3 ) substituents in a subsequent step.
Topics & Concepts
Allylic rearrangementElectrophileChemistryStereocenterVinylsilaneSilylationStereochemistryMedicinal chemistryAsymmetric inductionAlkylCatalysisEnantioselective synthesisOrganic chemistryAsymmetric Synthesis and CatalysisCatalytic Cross-Coupling ReactionsOrganoboron and organosilicon chemistry