The Anderson rearrangement

Dehydrohalogenation reactions of complex salts that contain metal halide anions and onium cations were first discovered by Anderson in 1855.3/4 Almost immediately after the discovery of pyridine, Anderson prepared pyridinium hexachloroplatinate(IV), [pyHlaiPtClg], and observed its conversion in aqueous solution to [PtCl4(py)2].3 Werner explained this 

Currently, a host of related solid state transformations are known. The Anderson rearrangement is, in general, a substitution of inner sphere ligands by outer sphere ligands. It has been demonstrated that heating a wide range of salts, [amineH]2[MX4] (M = Pd, Pt X = Cl, Br), in the solid state results in the formation of ds-[MX2(amine)2] (see Peyrone s rule. Chapter 1), Eq. 12.1  

such substitution reactions proceed both in the solid state and in solution in the manner predicted by the trans-effect. Peyrone s rule (Chapter 1) sometimes appears to be violated since isolated products may have undergone geometric isomerization subsequent to the initial thermal transformation. 

At the onset temperature of the Anderson rearrangement, measured by thermogravimetry, the reaction rate is already significant. Consequently, the onset temperatures of rearrangements can be used to indirectly estimate the relative rates of similar processes. 

The relationship between the onset temperatures of the Anderson rearrangement and the pKa of the amines was first shown for [amineHl2[PtCl4] complex. From reported experimental data it was shown that dre compounds could be divided into two groups compounds with an 

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It has been found that the Anderson rearrangement (Chapter 12) of [bipyH2][CoCl4] when the solid state is heated results, initially, in the formation of a polymeric complex with chloride bridges and an octahedral geometry about the metal centers, Eq. 11.4 ... 

The Anderson rearrangement reactions of [amineH]2[PtCl4(OH)2] (amine = ammonia, methylamine, pyridine, 3-methylpyridine, piperidine, quinoline) complexes, have been studied, Eq. 12.2 ... 

The dehydrohalogenation and dimerization of fr< s-[PtCl2L(DMSO)] (L = 3-methyl-4-acetyl-5-aminop)n azole) has been studied, Scheme 12.2. The product has been characterized by X-ray crystallography. The dehydrohalogenation is, in fact, an unusual variant of the Anderson rearrangement. Thus, it is a tertiary, inner-sphere nitrogen, and not a quaternary, outer-sphere nitrogen, that is subject to deprotonation and Pt-N bond formation. 

In a similar way, halide complexes of Pd(II) and Pt(II) with appropriate ligands are subject to the Anderson rearrangement and ring-closure in a single step,45 Scheme 12.10 ... 

Prasad RS, Anderson CE, Richards CJ, Overman LE (2005) Synthesis of tert-leucine-derived cobalt oxazoline palladacycles. Reversal of palladation diastereoselectivlty and application to the asymmetric rearrangement of N-aryl trifluoroacetimidates. Organometallics 24 77-81... 

The first stage in this process is likely to be an Anderson rearrangement, followed by deprotonation of the coordinated ammine. The complex [NH4]2[TcF5l has been shownSO to be subject to a similar transformation. 

C content [Stevenson (99) Anderson and Avery (24) ]. If no skeletal rearrangements occur in the mass spectrometer ion source, it is very easy to see how the position of the l3C atom can be obtained from the relative... 

In 1960, Anderson and Reese [1] reported that cathecol monoacetate (1) undergoes rearrangement to 2,3- and 3,4-dihydroxyacetophenone (2 and 3, respectively) upon illumination with ultraviolet (UV) light (Scheme 1). This report was the first one of a long list of articles and reviews [2-16] dealing with the photorrerarrangement of aromatic esters, which was extended to amides, carbonates, carbamates, thioesters, sulfonates, and related compounds. 

The present work deals with the photo-Fries rearrangement (PFR) and covers the literature appearing since the first report of Anderson and Reese to the beginning of 2002. It includes both the mechanistic aspects and the synthetic applications of this reaction. The topic of the PFR in polymers is also treated. In addition, a section has been devoted to the photo-Fries rearrangement in organized media, a field of recent interest. 

Method b Compounds B with a side-chain R of the type COCH2X (X = Cl or Br) (formed by a Hoesch condensation or Fries rearrangement from a corresponding molecule of t3rpe A) result in 3(2H)-benzofuranones (von Auwers-Shriner-Anderson reaction). 

An Amadori rearrangement product apparently was formed in the reaction of 3-C-phenylglyceraldehyde with V-methylaniline in dry ethanol-acetic acid solution as conducted by Smith and Anderson. A white, crystalline l-deoxy-l-(V-methylanilino)-3-C-phenylketose, C6H6(CH3)N C3H402-C6H6, was isolated. Whether the carbonyl group (the. compound... 

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