Dear phth,
I really appreciate your hard work, in order to collect and post all these documents. However, as hardly as I have tried, I cannot find anything therein that is against the HSAB theory.
1). AcAcOEt is not exactly the same as AcAcOH, where the hard base keeps the right to prefer to react with the hard carboxylic acid instead of the borderline enol acid and the borderline C-H acid; while in the case of AcAcOEt, there is competition between of the enol and the C-H borderline acids.
Always remember that the terms: acidity, basicity, electronegativity, polarizability and atoms/ions size are relative meanings.
2). The solvent effects towards enol/ketone equilibrium, as well as towards driving of parallel reactions, are well known. But remember that in addition to other interfering factors (e.g. H-bonding, polarizability changes, etc.), the strength of acids and bases significantly varies within different solvent media.
3). I am not talking about TiCl4 but about the formation of ketones silyl ethers. Anyway, in the posted reaction the tertiary chloride is leaving in Lewis acidic conditions, by Sn1 mechanism and forms a hard carbocation acid which prefers to react with the hard amine base site instead of the borderline carbanion site of the cyanide anion (Do not confuse hard adamantane carbocation acid with the phenyl carbocation, which a borderline acid, due to the aromatic conjugation).
4). HSAB theory is not applicable in Cope type rearrangement and peryciclic reactions that are perfectly explained by the Woodward-Hoffmann rules. HSAB theory is just a theory and not a principle, nor a theorem, neither a doctrine. Theories are susceptible to limitations and exceptions and have a well determined applicability range. Application of theories out of their applicability range, leads to extremities and mistakes. Your favorite publication is an assay to overcome the limitations, the exceptions and the extremities of the HSAB theory and thus, well done to be published. But, as mentioned above, it is too early for final conclusions. Besides, this a unique publication against thousands on HSABs and their proven applications in various sectors, biological sciences included.
5). Grignard reactions are nucleophilic attacks to the carbonyl and not radical reactions. The radical step is the initial incorporation of magnesium into alkyl(aryl) halide molecule. Once started the Grignard reaction, it cannot be stopped by the addition of a radical scavenger, in the second step. Besides, if you use pre-prepared Grignards (e.g. from Aldrich), you do need to add iodine crystals.
6a). By ending, please, do not be so fanatic with science but always keep a doubt, exactly as the authors of your favorite publication, did.
6b). Please also, do not be the first one who adopts a new theory, nor the last one who abandons an old theory (Except, if the new theory inventor is your class professor or your thesis supervisor).
Best Regards.