P(PhCH(2)NCH(2)CH(2))(3)N: an efficient lewis base catalyst for the synthesis of propargylic alcohols and Morita-Baylis-Hillman adducts via aldehyde alkynylation.
P(PhCH(2)NCH(2)CH(2))(3)N: an efficient lewis base catalyst for the synthesis of propargylic alcohols and Morita-Baylis-Hillman adducts via aldehyde alkynylation.
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DOI：
10.1021/jo9012332
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发表时间：
2009-07
期刊：
影响因子：
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通讯作者：
K. Wadhwa;V. Chintareddy;J. Verkade
中科院分区：
文献类型：
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作者：
K. Wadhwa;V. Chintareddy;J. Verkade
P（PhCH（2）NCH（2）CH（2））（3）N（1a）是一种有效的催化剂，可用于芳基三甲基硅基炔与芳香族、脂肪族和杂环醛在室温下的加成反应。反应条件温和，采用低催化剂负载（约100%）。5摩尔%）。只有炔丙醇被隔离在良好的优秀的分离产率时，富电子，电子中性，杂环，和脂肪族醛，而β-支化的森田-贝利斯-希尔曼（MBH）型加合物被隔离与电子不足的芳香族醛后，传统的酸水解的TMS醚产品。含有带有吸电子或供电子取代基的杂环和芳香基团的炔与环己甲醛和富电子芳香醛进行干净的加成，以优异的分离产率得到炔丙醇。当使用缺电子芳香醛时，分离出β-支化Morita-Baylis-Hillman（MBH）型加合物。两种类型的产品的反应途径提出。
Proazaphosphatrane P(PhCH(2)NCH(2)CH(2))(3)N (1a) is an efficient catalyst for the addition of aryl trimethylsilyl alkynes to a variety of aromatic, aliphatic, and heterocyclic aldehydes in THF at room temperature. The reaction conditions are mild and employ a low catalyst loading (ca. 5 mol %). Only propargylic alcohols were isolated in good to excellent isolated yields when electron-rich, electron-neutral, heterocyclic, and aliphatic aldehydes were employed, whereas beta-branched Morita-Baylis-Hillman (MBH) type adducts were isolated with electron-deficient aromatic aldehydes after conventional acid hydrolysis of the TMS ether products. Alkynes containing heterocyclic and aromatic groups bearing electron-withdrawing or -donating substituents underwent clean addition to cyclohexanecarboxaldehyde and to electron-rich aromatic aldehydes to give propargylic alcohols in excellent isolated yields. beta-Branched Morita-Baylis-Hillman (MBH) type adducts were isolated when electron-deficient aromatic aldehydes were employed. Reaction pathways to both types of products are proposed.