Monoallylation of 1,2-Diols by Pd/Sn Bimetallic Catalysis
Monoallylation of 1,2-Diols by Pd/Sn Bimetallic Catalysis
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Pd/Sn 双金属催化 1,2-二醇的单芳基化
DOI：
10.1002/chem.201102709
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发表时间：
2012
期刊：
影响因子：
--
通讯作者：
O.
中科院分区：
文献类型：
--
作者：
Kuriyama;M.; Takeichi;T.; Ito;M.; Yamasaki;N.; Yamamura;R.; Demizu;Y.; Onomura;O.
1，2-二醇的选择性转化在有机合成中具有重要意义，目前已报道了多种1，2-二醇的选择性单烷基化方法，但大多数情况下需要过量的1，2-二醇。[1]在过去，已经开发了许多化学计量的方法，例如缩醛的还原裂解，[2]使用聚合物树脂，[3]铊盐，[4]三氧化二铊盐，[5]银氧化物，[6]二丁基氧化锡，[7]芳基硼酸，[8]和通过分子内脱氢卤-ACHTUNGTRENNUNG直接烯丙基化1，2-二醇。[9]另一方面，只有少数催化反应被报道，使用二氯化锡，[10]钯盐，[11]相转移催化剂，[12]和冠醚的成功例子有限。[13]特别地，1，2-二醇的选择性单烯丙基化在这些类型的转化中是非常重要的，因为烯丙基基团可以用作保护基团和可转化的合成立足点。然而，在催化方法中没有报道1，2-二醇的成功单烯丙基化。[2-13]最近，我们报道了以二氯化二甲基锡[14]或ACHTUNGTRENNUNG（II）铜盐[15]为催化剂进行1，2-二醇单酰化的有效方法，并开发了以氯化亚铜（II）或芳基硼酸催化的1，2-二醇选择性单烷基化。[16]然而，这些催化剂对1，2-二醇的单烯丙基化反应的催化活性不足，底物范围较窄。因此，我们研究了其他催化剂体系，发现由过渡金属和刘易斯酸组成的组合催化剂有效地促进了1，2-二醇的单烯丙基化。在此，我们描述了有效的选择性单烯丙基化的1，2-二醇的Pd/Sn双金属催化剂。
Selective transformation of 1, 2-diols is highly important in synthetic organic chemistry and a variety of methods for the selective monoalkylation of 1, 2-diols have been reported, which required an excess amount of 1, 2-diols in most cases.[1] In the past, many stoichiometric methods have been developed, such as reductive cleavage of acetals,[2] use of polymer resins,[3] thallium salts,[4] monosodium salts,[5] silver oxide,[6] dibutyltin oxide,[7] arylboronic acids,[8] and direct allylation of 1, 2-diols through intramolecular dehydrohalo-ACHTUNGTRENNUNGgenation.[9] On the other hand, only a few catalytic reactions were reported with limited successful examples using tin dichloride,[10] palladium salts,[11] phase-transfer catalysts,[12] and crown ether.[13] In particular, selective monoallylation of 1, 2-diols is quite important in these types of transformation because the allyl group can be utilized as a protecting group and convertible synthetic foothold. However, no successful monoallylation of 1, 2-diols have been reported in catalytic methods.[2–13]Recently, we reported the effective methods for monoacylation of 1, 2-diols with dimethyltin dichloride [14] or copper-ACHTUNGTRENNUNG (II) salts [15] as catalysts and also developed the selective monoalkylation of 1, 2-diols catalyzed by copper (II) chloride or arylboronic acids.[16] However, these catalysts gave insufficient catalytic activity with only a narrow scope of substrates for monoallylation of 1, 2-diols. Therefore, we examined other catalyst systems and found that combined catalysts composed of a transition metal and Lewis acid promoted monoallylation of 1, 2-diols effectively. Herein, we describe the efficient selective monoallylation of 1, 2-diols by Pd/Sn bimetallic catalysis.