On the physical interpretation of Heywood and Redhead's algebraic impossibility theorem

Heywood and Redhead's 1983 algebraic (Kochen-Specker type) impossibility proof, which establishes the inconsistency of a broad class of contextualized local realistic theories, assumes two locality conditions and two auxiliary assumptions. One of those auxiliary conditions, FUNC^*, has been called a physically unmotivated,ad hoc formal constraint.In this paper, we derive Heywood and Redhead's auxiliary conditions from physical assumptions. This allows us to analyze which classes of hidden-variables theories escape the Heywood-Redhead contradiction. By doing so, we hope to clarify the physical and philosophical ramifications of the Heywood-Redhead proof. Most current hidden-variables theories, it turns out, violate Heywood and Redhead's auxiliary conditions.1. See Redhead [1], pp. 133–136, for a complete discussion.2. Arthur Fine first pointed out the implicit reliance on FUNC^*, and proved FUNC^* to be both consistent with and independent of the Value Rule.3. LetA=_ia_i P _i andB=_jb_j P_j be spectral resolutions ofA andB. Then <A,B> is the observable associated with maximal operatorR=_ijf_ij P _iP_j, where f_ij=F(a_i,b_j), and where function F is 1:1.4. Heywood and Redhead's versions of these conditions employ equivalence-class notation to specify the ontological context. {<D,E>}={R} refers to the equivalence class of all possible <D,E> formed by using different F functions (cf. Footnote 3). Clearly, such notation assumes that ifR andR are two distinct commuting maximal operators formed as described in Fn. 3 fromD andE using two different F(d_i,e_j) functions, then [Q]^t _(R)(R)=[Q]^t _(R)(R), so that [Q]^t _{R}(R) is uniquely defined.Heywood and Redhead never rely upon this assumption in their proof, however. It is easily checked that a Heywood-Redhead contradiction follows from my non-equivalence class versions of OLOC, ELOC, VR, and FUNC^*. Therefore, I will not use equivalence class notation.5. Here I denote by µ_R the composite state of all the apparatuses needed to measure R. So µ_R may represent the state of more than one device.6 This is because in a hidden-variables framework, quantum mechanical probabilities are a weighted average of the underlying hidden-variables probabilities.7. This argument resembles a proof given by Fine [8].8. Recall from theorem 1 that ifQ=f(R), then for all quantum states , P_(t)(Qf(r), R=r)=0.     

N-α-Benzyloxyacetyl derivatives of (S)-4-benzyl-5,5-dimethyloxazolidin-2-one for the asymmetric synthesis of differentially protected α,β-dihydroxyaldehydes

α-Dibenzylamino- and α-benzyloxy- derivatives of N-acetyl-(S)-4-benzyl-5,5-dimethyloxazolidin-2-one readily undergo highly stereoselective boron mediated syn-aldol reactions with a range of aromatic and aliphatic aldehydes, generating the syn-aldol products in good to excellent yields as single diastereoisomers after purification. In the α-dibenzylamino series, deprotection of the functionalised aldol fragments to the corresponding α-amino-β-hydroxy methyl ester or α-amino-β-hydroxyaldehyde proved problematic, with a range of N- and O-protecting groups giving mixtures of products arising from endocyclic and exocyclic cleavage pathways. However, in the α-benzyloxy series, O-silyl protection of the aldol products, and subsequent DIBAL reduction gives stereoselectively the corresponding N-1′-hydroxyalkyloxazolidin-2-ones, which undergo base promoted fragmentation to the desired highly functionalised and differentially protected α,β-dihydroxyaldehydes in good yields and without loss of stereochemical integrity.     

Rhodathiaboranes with `anomalous' electron counts: synthesis, structure and reactivity

Analysis of the structures of 8,8-(PPh₃)₂-8,7-nido-RhSB₉H₁₀ and 9,9-(PPh₃)₂-9,7,8-nido-RhC₂B₈H₁₁ by RMS misfit calculations has confirmed that these rhodaheteroboranes possess nido 11-vertex cluster geometries in apparent contravention of Wade's rules. However, examination of the molecular structures of both species shows that the {RhP₂} planes are inclined by ca. 66° with respect to the metal-bonded SB₃ or CB₃ faces, and that two weak ortho-CHRh agostic interactions occupy the vacant co-ordination position thereby created. As a consequence of these agostic bonds the Rh atom, and hence the overall cluster, is provided with an additional electron pair, meaning that their nido structures are now fully consistent with Wade's rules. The chelated diphosphine compound 8,8-(dppe)-8,7-nido-RhSB₉H₁₀ is similar to the PPh₃ compound in showing the same agostic bonding. Attempts to prepare a bis-P(OMe)₃ analogue result in ligand scavenging and the formation of 8,8,8-{P(OMe)₃}₃-8,7-nido-RhSB₉H₁₀. Similarly, reaction between Cs[6-arachno-SB₉H₁₂] and RhCl(dmpe)CO does not result in CO loss but in formation of 8,8-(dmpe)-8-(CO)-8,7-nido-RhSB₉H₁₀, shown to exist as a mixture of two of three possible rotamers. Deprotonation of 8,8-(PPh₃)₂-8,7-nido-RhSB₉H₁₀ and 8,8-(dppe)-8,7-nido-RhSB₉H₁₀ with MeLi yields the anions [1,1-(PPh₃)₂-1,2-closo-RhSB₉H₉]⁻ and [1,1-dppe-1,2-closo-RhSB₉H₉]⁻, respectively, with octadecahedral cage structures. It is argued that anion formation causes the agostic bonding to be `switched-off' and results in the cluster adopting the closo architecture predicted by Wade's rules. This structural change is fully reversible on reprotonation, and if reprotonation of [1,1-(dppe)-1,2-closo-RhSB₉H₉]⁻ is carried out in MeCN, the product 8,8-(dppe)-8-(MeCN)-8,7-nido-RhSB₉H₁₀ forms. Interestingly, 8,8-(dppe)-8-(MeCN)-8,7-nido-RhSB₉H₁₀ reconverts to 8,8-(dppe)-8,7-nido-RhSB₉H₁₀ on standing in CDCl₃, suggesting that the agostic bonding is sufficiently strong to displace co-ordinated MeCN. All new compounds are fully characterised by multinuclear NMR spectroscopy and, in many cases, by single crystal X-ray diffraction.     

The synthesis of 1,4-diazacycl[3,2,2]azine

The diazaanalog of “cycl[3,2,2]azine”, “1,4-diazacycl[3,2,2]azine” (1,4,7b-triazacyclopent-[cd]indene) and its 2-methyl derivative were prepared. These compounds are subject to facile acid-catalyzed hydrolysis affording substituted imidazo[1,2-a]pyridines.