Highly enantioselective and regioselective nickel-catalyzed coupling of allenes, aldehydes, and silanes.
A complex derived from Ni(cod)2 and NHC-IPr catalyzes a three-component coupling reaction involving allenes, aldehydes, and organosilanes and transfers the axial chirality of the allene to a stereogenic center in the product with very high fidelity. An unexpected regioselectivity is observed; favored are allylic rather than homoallylic alcohol derivatives, corresponding to the unusual process of coupling two electrophilic atoms: the allene sp and aldehyde carbon atoms. In all cases, high enantioselectivity, high Z/E selectivity, and, with differentially substituted allenes, high site selectivity are observed. This transformation represents the first enantioselective multicomponent coupling process of allenes.
Ng
Sze-Sze
SS
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, 02139, USA.
Jamison
Timothy F
TF
D000447:Aldehydes / Q000737:chemistry*; D000466:Alkadienes / Q000737:chemistry*; D002384:Catalysis; D009532:Nickel / Q000737:chemistry; D009930:Organic Chemicals / Q000138:chemical synthesis*; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism
D000447:Aldehydes; D000466:Alkadienes; D009930:Organic Chemicals; D012821:Silanes; C025947:propadiene; D009532:Nickel