Anderson rearrangement

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 ... 

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 ... 

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... 

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 ... 

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. 

Anderson CE, Overman LE (2003) Catalytic asymmetric rearrangement of allylic trichlor-oacetimidates. A practical method for preparing allylic amines and congeners of high enantiomeric purity. J Am Chem Soc 125 12412-12413... 

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... 

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. 

Anderson GH, Smith J. Acid-catalyzed rearrangement of hydroperoxides. II. Phenylcycloalkyl hydroperoxides. Can J Chem 1968 46 1561-1570. 

Lai, G. Anderson, W. K. A concise synthesis of a benzimidazole analogue of mycophenolic acid using a BF3-Et20 catalyzed amino-Clai-sen rearrangement. Tetrahedron Lett. 1993, 34, 6849-6852. 

Anderson, J.C. and Reese, C.B. (1962) Photo-induced rearrangement involving aryl participation. Tetrahedron Letters, 3, 1-4. 

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). 

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