Given the unique success of hydrogen bond donors in promoting reactivity and selectivity (Table and Scheme 2), we propose the model for enantioinduction depicted in Scheme 3A. Hydrogen bonding between the acceptor nitro group and the donor thiourea helps "fix" the olefin conformation; attack by the pendant silanol is followed by deprotonation by the basic arm of the bifunctional catalyst. Given that this cyclization is essentially a cyclo-isomerization under thermodynamic control, we were certainly amazed that products could be obtained in excellent yields and enantioselectivities for a variety of substrates (Scheme 2)! What underlies the difficulties with certain nitro-styrenes bearing substrates ortho to the nitro-olefins (Scheme 2, Products 16-18)? We propose that steric-clashing (Scheme 3B) forced the nitro-olefin into a conformation that precluded productive interaction with the chiral thiourea. However, this conformation did prevent interaction with the less discriminative urea and squaramide catalysts, allowing for exracemic We were pleased that our optimized protocol was scalable from 0.1 mmol to 1 mmol (10-fold increase) without much difference in yield or selectivity (Scheme 4A) and that the products were synthetic intermediates for further transformations (Scheme 4B). The nitro-group could be converted into an by reduction with a combination of NiCl2 and NaBH4 48 ; for ease of isolation, the amine was immediately protected with Boc2O. Excision of the silyl moiety with TBAF provided enantio-enriched amino alcohols (Products 26 and 28). These amino alcohols could be further transformed. For example, the aromatic ring of 28 was brominated using our laboratory's NaBr/Selectfluor protocol. In summary, we show the first racemic and scalemic examples of di-tert-butyl silanoxy Michael additions. Our operationally simple protocol is selective for nitro-olefins and simply involves stirring substrate with an appropriate hydrogen-bond donor catalyst without any special precautions to exclude air or moisture. For each substrate examined, we have developed complementary protocols which respectively optimize yield and enantioselectivity. Our reactions scale well, and the products are valuable intermediates for further transformations, including for the preparation of enantioenriched vicinal amino-alcohols. Given the ubiquity of such compounds in academic and industrial chemistry, we expect that our protocols will be welcome additions to existing technology.