High-77 cuprates

Keywords High-77, cuprates, stripes, inhomogeneities, pairing symmetry, Mott transition... 

I present here some of the highlights of the structure-property relations in the various families of high cuprates and illustrate how chemistry plays a major role in the development of such important materials and how solid state chemistry constitutes a fascinating and important branch of chemical science in its own right. 

Anderson, P.W., 1997, The Theory of Superconductivity in High Cuprates (Princeton University Press, Princeton, NJ). 

I lO] Anderson P W 1997 The Theory of Superconductivity in the High-Ti Cuprates (Princeton Series in Physics) (Prinoeton Prinoeton University Press)... 

CUO2 layers appear in all cuprate superconductors and appear to be a necessary but not sufficient condition for high temperature superconduction. The La2SrCu20g 2 compound has CUO2 layers but does not superconduct. Experiments also indicate that T is proportional to the carrier density in the CUO2 layer but not to the volume carrier density, which is further evidence that the YBa2Cu202 is a two-dimensional superconductor. 

The formation of g-alkyl-a,g-unsaturated esters by reaction of lithium dialkylcuprates or Grignard reagents in the presence of copper(I) iodide, with g-phenylthio-, > g-acetoxy-g-chloro-, and g-phosphoryloxy-a,g-unsaturated esters has been reported. The principal advantage of the enol phosphate method is the ease and efficiency with which these compounds may be prepared from g-keto esters. A wide variety of cyclic and acyclic g-alkyl-a,g-unsaturated esters has been synthesized from the corresponding g-keto esters. However, the method is limited to primary dialkylcuprates. Acyclic g-keto esters afford (Zl-enol phosphates which undergo stereoselective substitution with lithium dialkylcuprates with predominant retention of stereochemistry (usually > 85-98i )). It is essential that the cuprate coupling reaction of the acyclic enol phosphates be carried out at lower temperatures (-47 to -9a°C) to achieve high stereoselectivity. When combined with they-... 

As well as the modified cuprate reagents, Grignard reagents in the presence of the highly sterically demanding methylaluminum bis(2,4,6-tri-fcrr-butylphenoxide) (MAT, 8) also show considerable anti-Cram selectivity35 36 (Table 9). 

The /J-amino aldehyde 1. readily available from aspartic acid, is configurationally very stable. No epimerization of the stereocenter is observed upon addition of Grignard Or cuprate reagents and the transformations display relatively high levels of 1,3-asymmetric induction73. This C-3-directing effect is superimposed upon the 1,2-directing effects of the C-2-substituents (Rl). 

The titaniated (25)-2,5-dihydro-2-isopropyl-3,6-dimethoxypyrazines derived from cyclo(L-Val, Gly) or cyclo(L-Val, Ala) (1, R1 = H, CH3) react with a,/I-unsaturatcd aldehydes exclusively by 1.2-addition (cf. nearly exclusive 1,4-addition of ,//-unsaturated ketones with cuprate complexes of 2,5-dialkoxy-3,6-dihydropyrazines, see Section D. 1.5.2.3.1.4.) in a highly diastereoselective mode to give virtually only the (l S,2R)-diastereoniers 2 ". In reactions with the corresponding lithiated pyrazines both regioselectivity and diastereofacial differentiation at C-2 are also remarkably high (dc 95 %), but the diastereomeric excess at C-l is substantially smaller (30 50%) ... 

The reaction of propargylic chiral acetals with a catalytic copper reagent (RMgX/5% CuX) provides the expected alkoxy allenes in quantitative yield (Table 3)61. The diastereomeric excess is highly dependent on the size of the ring of the acetal and on the type of substituents it contains. The best diastereomeric excess is 85% with the acetal derived from cyclooctanediol. The use of lithium dimethylcuprate results in 1,2-addition lo the triple bond and the resulting lithium alkenyl cuprate bearing a cyclic acetal does not eliminate even at reflux temperature ( + 35°C). 

The reaction of 3-substituted 3-haloallenes with various cuprates, the converse reaction of propargyl derivatives, proceeds in an SN2 manner to form alkynes 69b. Very high anti stereoselectivity is achieved693. 

This 1,2-asymmetric induction has been attributed to stcric and stcrcoclectronic factors. Similarly, the cuprate additions to 4-alkylcyclopentenones l7 -19, and 4-alkylcyclohexcnones16 b-18 proceeded with very high trans diastereoselection. The copper iodide catalyzed addition of propylmagnesium bromide to 4-methyl-2-cyclohexenone gave a trans/cis ratio of 80 20, whereas the addition to 5-methyl-2-cyclohexenone produced a transjcis ratio of 93 72 3-Silyloxy system 3 gave the trans-adduct 4 on treatment with butylcopper-boron trifluoride reagent20. 

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