Synthesis of stereopentad analogues of the C14-C22 segment of callystatin A through additions of chiral allenylzinc reagents to stereotriads.
Synthesis of stereopentad analogues of the C14-C22 segment of callystatin A through additions of chiral allenylzinc reagents to stereotriads.
复制标题
通过向立体三联体中添加手性丙二烯基锌试剂来合成 callystatin A C14-C22 片段的立体五联体类似物。
DOI：
10.1021/jo015936k
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发表时间：
2001
期刊：
影响因子：
--
通讯作者：
Schaaf,GM
中科院分区：
文献类型：
--
作者：
Marshall,JA;Schaaf,GM
通过 Pd 催化 (R)-和 (S)-3-丁炔-2-醇甲磺酸盐金属化原位制备的 (P)-和 (M)-丙二烯基锌试剂添加到 syn,syn, syn,anti, anti,anti 和 anti,syn 立体化学的非对映立体三元醛 8,13,18 和 23 中。前两种醛的加成提供了具有高非对映选择性和可忽略不计的错配的四种反加合物。后两种醛和 (M)-丙二烯基锌试剂观察到显着的错配。考虑空间和偶极控制元素，对可能的过渡态进行了评估。
The addition of (P)-and (M)-allenylzinc reagents, prepared in situ through Pd-catalyzed metalation of (R)-and (S)-3-butyn-2-ol mesylates, to diastereomeric stereotriad aldehydes8,13,18, and23of syn,syn, syn,anti, anti,anti, and anti,syn stereochemistry was examined. Additions to the former two aldehydes afforded the four anti adducts with high diastereoselectivity and negligible mismatching. Significant mismatching was observed with the latter two aldehydes and the (M)-allenylzinc reagent. An evaluation of possible transition states is presented in consideration of steric and dipolar control elements.