42 1,1'-Binaphthyl-2,2'-diyl Phosphoryl Chlorideの不斉認識性による絶対配置の決定(口頭発表の部)
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概要
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The chirality of the secondary carbon atom attached to the alcohol group can be decided with high sensitivity by derivation into a 1,1'-binaphthyl-2,2'-diyl phosphate. The secondary alcohol and 1,1'-binaphthyl-2,2'-diyl phosphoryl chloride ((BNP)Cl) with the same chirality react preferentially over that with different chirality. The result is characteristically confirmed by the CD spectrum. since the binaphthol moiety causes a Davydov splitting with a very strong intensity. The chirality recognition ability of the BNP reagent is not affected by ring size, neighboring functional groups, or the configuration of the hydroxyl group, and especially exhibited with acyclic alcohols, as well as the cyclic compounds. Chirality of the asymmetric carbon atom attached to the hydroxy methylene group can be also determined with high sensitivity by derivation into the (R,S)-BNP ester. The BNP derivatives are not consistent with the sign of their CD spectra and the chirality of the asymmetric carbon atom. The inconsistent result disappears with the introduction of a verso sequence rule. The concept is that, in a bond formation reaction, the hydroxy methylene group on a reaction axis is excluded from the priority, and the three other ligands on the chiral carbon atom are put into a priority sequence and reassigned the novel chiral label (R) or (S). The sign of the (R,S)-BNP derivatives consequently accords with the verso chirality of the asymmetric carbon atom.
- 1990-09-25