Attempting to overcome this, our strategy for the in-situ generation of keto-aldehydes shifted from reduction to oxidation. 5-Oxohexanol and 6-oxoheptanol were synthesised and found to be active substrates for AcCO6. Subjecting these substrates to identical conditions to those utilized in the terminal diol work yielded a range of asymmetric heterocycles (Table ). Where possible, ee and absolute configuration were determined using chiral GC-FID, although these assignments are largely limited due to challenges in achieving the separation of non-derivitizable products and accessing enantiomerically pure standards. For the synthesis of α-substituted N-heterocycles, the AcCO6-RedAm cascade methodology proved more amicable to optimization and conditions were determined for the reactions to be performed on scale. Preparative scale synthesis was again performed on 1 mmol scale with (S)-N-cyclopropyl-2-methylpiperidine (13i) isolated in good yield and ee following distillation (Scheme 4).