Although the precedent described above suggested a very low likelihood of success, an extensive exploration under a variety of MHAT conditions for the hydronitration of alkene 23 with numerous potential •NO2 donors (28-33, 35A/B, 16, entries 1-9, and others as listed in the SI) was pursued, as partly summarized in Table . Mn-, Fe-, and Co-based catalysts were all evaluated at the outset with Co-salen complexes being identified as the most promising starting point. Nitrating agent candidates were chosen from the literature based on their bench-stability and precedent for use in aromatic nitration and alkene difunctionalization. For instance, saccharin-based reagent 28 (entry 1) along with inexpensive Co II (salen)-I delivered 17% of the desired nitrated product 27. Unfortunately, this was one of the minor adducts, accompanied with significant quantities of isomerized olefin 24, alkane 25, and tertiary alcohol 26 (anaerobic Mukaiyama hydration ). It was reasoned that the reagent structure would have the most profound impact on the ratio between 26 (arising from a Path A mechanism, vide supra) and the desired nitro compound 27. Several additional known reagents were thus screened such as hydantoin 29 (entry 2), succinimide 30 (entry 3), pyrazole 31 (entry 4), tetranitromethane 32 (TNM, entry 5), and cyclohexadienone 33 (entry 6) furnished either no desired product or 26 as the major adduct. Given the high reactivity observed with anomeric amide-based halogenating reagents we reasoned that a similar boost in reactivity might translate to the corresponding anomeric nitroamides. Unfortunately, all attempts to prepare an analogous anomeric nitroamide (such as 34) failed due to the instability of the resulting products via rearrangement pathways (Table , top right, see SI for details). Eventually it was discovered that exchanging the N-O for an N-N bond in such structures led to enhanced stability (35A/B, 16, see SI for additional analogs). To our knowledge, no such structures have ever been prepared despite their simple synthesis via the corresponding hydrazides in two simple steps without any chromatography. Anomeric nitroamide 35A (entry 7) showed promise delivering 27 in 30% yield albeit as a 1:1 mixture with 26.