DIASTEREOSELECTIVE SYNTHESIS OF PHYCOCYANOBILIN CYSTEINE ADDUCTS
DIASTEREOSELECTIVE SYNTHESIS OF PHYCOCYANOBILIN CYSTEINE ADDUCTS
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DOI：
10.1021/ja00021a032
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发表时间：
1991-10-09
影响因子：
15
通讯作者：
RAPOPORT, H
中科院分区：
文献类型：
--
作者：
BISHOP, JE;NAGY, JO;RAPOPORT, H
介绍了半胱氨酸连接的藻蓝胆素衍生物的两种非对映体的合成方法。 关键的反应是半胱氨酸甲酯与适当的二氢吡咯甲酮离析物的非对映选择性1，6-迈克尔加成。 然后将如此产生的非对映体加工成两种藻蓝胆素三甲酯。 通过应用ROESY NMR实验完成相对立体化学，双键几何形状和溶液构象的连续分配，而绝对立体化学分配基于已知手性的化合物的降解。
Methodology is presented for the synthesis of two diastereomers of a cysteine-linked phycocyanobilin derivative. The crucial reaction is a diastereoselective 1,6-Michael addition of cysteine methyl ester to an appropriate dihydropyrromethenone educt. The diastereomers so generated were then elaborated to two phycocyanobilin trimethyl esters. Definitive assignments of relative stereochemistry, double bond geometry, and solution conformation are accomplished by application of ROESY NMR experiments, while absolute stereochemical assignments are based on degradation to compounds of known chirality.