Finally, to investigate the chemoselectivity of 4 towards alkenes or alkynes, we treated 4 with 2methylbut-1-en-3-yne, a conjugated enyne (Scheme 6, bottom-right). Examination of the 1 H-NMR spectrum (THF-d 8 , see ESI Section 1.10) revealed full conversion of 4, yielding 8. Similar to 5, a downfield singlet resonance at δ = 7.15 ppm that shows a 1 H- C ASAP-HMQC cross-peak with a carbon resonance at δ = 152.3 ppm (vs. δ = 7.38 and 150.5 ppm found for 5), are indicative of preferential addition of the alkyne moiety to the NHGe over the alkene moiety. Consistent with this assignment, two singlet resonances in the alkene region of chemical shift are found, which are bound to the same carbon atom (δ = 110.3, confirmed through 1 H-13 C ASAP-HMQC NMR), and were assigned to the terminal alkene protons.