Two decades after the seminal publications of List and Macmillan, it is now universally acknowledged that organocatalysts form the third pillar of asymmetric catalysis, along with enzymes and chiral organometallic complexes. Along with the tremendous spurt in the application of organocatalysts to a wide range of different transformations, there has also been a concerted effort to understand the mechanism(s) by which such asymmetric catalytic processes take place, both through experimental, as well as computational studies. This has helped improve the efficiency of the systems. Nevertheless, there are still some interesting aspects of organocatalytic systems that are yet to be completely understood. One such area is the use of additives: it has been observed that the presence of an additive leads to improvement in the yield, enantioselectivity, or both, in a wide variety of organocatalytic systems. Such additives include organic acids, chiral phosphoric acids, alcohols, water, amines, molecular sieves and salts. Of these, the most common are acids and alcohols. It has been hypothesized that their role in such systems is to increase the pKa of the reaction medium through their acidic nature. In some cases, they have been seen as proton shuttles. It has also been hypothesized in some instances that the additive could hydrogen bond with one of the substrates. However, researchers have wondered whether additives could have a more active, defined role in increasing the efficiency of organocatalytic systems. Such a possibility seems particularly pertinent when one considers the beneficial effect one additive class: that of aromatic additives, have played in organocatalytic systems. C-H activation via cross coupling between aryl iodides/bromides and the C-H bonds of arenes, mediated solely by the presence of 1,10-phenanthroline as catalyst in the presence of potassium tert-butoxide as a base, studied by Shi and coworkers, for instance, was seen to benefit from the presence of 1,10-phenathroline. Curran and Studer, commenting on this work, pointed out that the role played by 1,10-phenathroline as additive was unclear. There are several other interesting reports where aromatic alcohols such as phenol (substituted and unsubstituted) and naphthol, have been employed as additives, leading to improved yield and enantioselectivity. Chen and coworkers reported the α-thiocyanation of oxindole with the BzCPD catalyst, using 2-napthol as the additive. Feng and coworkers investigated the asymmetric nitroaldol reaction of αketophosphonates, employing 2,4-nitrophenol as the additive. Zhu, Masson and coworkers reported invertible enantioselectivity with the 6′-deoxy-6′-acylamino-beta-isocupredine catalyst in the asymmetric aza-Morita-Baylis-Hilman reaction, using β-napthol as the additive. Zhu et al. found that the addition of a small amount of β-naphthol in the aza-Morita-Baylis-Hillman reaction of imine and β-naphthyl acrylate led to improved yield and enantiomeric excess (ee). They considered the additive as a hydrogen bonding species. Chen and coworkers studied phenol-additive effects on the aza-MBH reaction of ketimines and acrolein: the addition of (R)or (S)-BINOL to the system as additive was found to dramatically improve the enantioselectivity. Fu and coworkers used 2-chloro-6-methylphenol as an additive in the phosphine-catalyzed double γ-addition of racemic heterocycles to racemic allenoates. Zanardiandcoworkersreportedswitchableregioselectivity in organocatalyticasymmetricadditiontoenals, using an aminecatalystandparanitrophenolasthe additive. Leitner andcoworkersreportedbifunctionalactivationandracemization in thecatalyticasymmetricaza-Morita-Baylis-Hilmanreaction, using PPh3 ascatalystand 3,5bis(CF3)phenolasthe additive. Ooi and coworkers have reported a supramolecular assembly system for the conjugate addition of azalactones to unsaturated acyl benzotriazoles, where three molecules of phenol were envisaged to participate through a hydrogen bonding network, This potential of the aromatic alcohols to stabilize both substrates leads to an important question: is it possible that the additive plays a previously unsuspected role in such systems, by explicitly participating in a cooperative fashion in the reaction, as a second catalyst? This is the question that has motivated the current computational investigation with density functional theory (DFT).