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    • 4. 发明申请
    • Cyclic ketones, their preparation and their use in the synthesis of amino acids
    • 循环酮,其制备及其在氨基酸合成中的应用
    • US20030187296A1
    • 2003-10-02
    • US10312065
    • 2003-02-05
    • David Clive BlakemoreJustin Stephen Bryans
    • C07C229/32C07C061/06C07C061/16
    • C07C229/28C07B2200/07C07C45/62C07C45/676C07C45/69C07C49/395C07C51/09C07C51/412C07C57/46C07C227/04C07C2601/08C07C49/597
    • A method is provided for making an enantiomerically pure of the formula: in which R and Rnull represent C1nullC10 alkyl, C2nullC10 alkenyl or C3nullC10 cycloalkyl and the wedges signify (S)- or (R)-stereochemistry, the substituents in compound (II) being trans. Conjugate addition is carried out between an organometallic nucleophile that provides a group R as defined above and (R)-4-acetoxycyclopent-2-en-1-one, (S)-4-acetoxycyclopent-2-en-1-one or a similar compound in which acetoxy is replaced by another leaving group to give, e.g. in the case of the acetoxy compound, a trans 3,4-disubstituted addition product of formula III or IV; The acetyl group is eliminated from the addition product to give an (R)- or (S)-4-alkyl or 4-alkenyl cyclopent-2-en-1-one the compound of formula is then to be hydrogenated to give a cyclopentanone of formula (I) or conjugate addition of a second organometallic nucleophile that provides a group Rnull as defined above to the compound of the above formula may be carried out to give a trans 3,4-disubstituted addition product of formula (II). One of the above compounds may be converted e.g. via an intermediate (XV)-(XVIII) (in which the substituents R and Rnull and the wedges have the meanings indicated above) to a gabapentin analogue of one of the formulae shown below: in which the substituents R and Rnull and the wedges also have the meanings indicated above. 1 2
    • 提供了一种制备具有下式的对映异构体纯的方法:其中R和R'代表C 1 -C 10烷基,C 2 -C 10烯基或C 3 -C 10环烷基,楔形表示(S) - 或(R) - 立体化学, 化合物(II)中的取代基是反式的。 在提供如上所定义的基团R的有机金属亲核试剂和(R)-4-乙酰氧基环戊-2-烯-1-酮,(S)-4-乙酰氧基环戊-2-烯-1-酮或(S)-4-乙酰氧基环戊-2-烯-1-酮之间进行共轭加成 类似的化合物,其中乙酰氧基被另一个离去基团取代,例如 在乙酰氧基化合物的情况下,式III或IV的反式3,4-二取代的加成产物; 从加成产物中除去乙酰基,得到(R) - 或(S)-4-烷基或4-烯基环戊-2-烯-1-酮,然后氢化得到环戊酮 可以进行式(I)化合物的共轭加成或向上述化合物提供如上定义的基团R'的第二有机金属亲核试剂的共轭加成,得到式(II)的反式3,4-二取代的加成产物。 上述化合物之一可以被转化为例如。 (XV) - (XVIII)(其中取代基R和R'和楔子具有上述含义)与下列通式所示的加巴喷丁类似物反应:其中取代基R和R'和 楔子也具有上述含义。 <化学 - cwu id =“CHEM-US-00002”> 2