Zn-catalyzed asymmetric allylation for the synthesis of optically active allylglycine derivatives.: Regio- and stereoselective formal α-addition of allylboronates to hydrazono esters
Zn-catalyzed asymmetric allylation for the synthesis of optically active allylglycine derivatives.: Regio- and stereoselective formal α-addition of allylboronates to hydrazono esters
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DOI：
10.1021/ja710627x
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发表时间：
2008-03-12
影响因子：
15
通讯作者：
Kobayashi, Shu
中科院分区：
文献类型：
--
作者：
Fujita, Mari;Nagano, Takashi;Kobayashi, Shu
我们发展了锌催化的亚肼基酯与烯丙基硼酸酯的不对称烯丙基化反应。该反应以高产率和高立体选择性顺利进行。值得注意的是，α-取代的烯丙基硼酸酯仅发生正式的α-加成，并观察到优异的立体选择性。这是第一个催化区域和立体选择性烯丙基化与正式的α-加成的例子。此外，反应在水性介质中进行，并且水的使用是必要的。Zn（OH）（2）可能是不对称烯丙基化反应的催化剂，并证实了Zn（OH）（2）的催化活性。这也是第一例手性金属氢氧化物催化的不对称反应。
We have developed Zn-catalyzed asymmetric allylation of hydrazono esters with allylboronates. The reactions proceeded smoothly in high yields and high stereoselectivities. Remarkably, formal alpha-addition occurred for alpha-substituted allylboronates exclusively, and excellent stereoselectivities were observed. This is the first example of catalytic regio- and stereoselective allylations with formal alpha-addition. In addition, the reaction proceeded in aqueous media, and the use of water is essential. Zn(OH)(2) might be a catalyst in this asymmetric allylation, and the catalytic activity of Zn(OH)(2) was confirmed. This is also the first case of chiral metal hydroxide-catalyzed asymmetric reactions.