Copper(I)-catalyzed asymmetric 1,6-conjugate allylation.
Copper(I)-catalyzed asymmetric 1,6-conjugate allylation.
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DOI：
10.1038/s41467-020-19293-9
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发表时间：
2020-10-30
影响因子：
16.6
通讯作者：
Yin L
中科院分区：
文献类型：
--
作者：
Shi CY;Pan ZZ;Tian P;Yin L
不饱和羰基化合物的催化非对称共轭烯丙基化通常难以实现，因为1,2加成是主要的，而高不对称诱导是一项具有挑战性的任务。在此，我们公开了铜(I)-NHC配合物催化2,2-二甲基-6-烷基- 4h -1,3-二恶英-4-酮的不对称1,6-共轭烯丙基化。在NHC配体中发现酚羟基是获得所需产物的关键。δ位置的芳基和烷基都具有良好的耐受性，相应的产物有中高收率和高对映选择性。此外，2-取代和3-取代的烯丙基硼酸盐均可作为可接受的烯丙基化试剂。最后，通过多用途末端烯烃和二恶英酮基团的转化，证明了该产品的合成用途。不饱和羰基化合物的催化非对称共轭烯丙基化通常由于1,2加成的竞争而难以实现。在这里，作者报道了铜(I)催化的2,2-二甲基-6-烷基- 4h -1,3-二恶英-4- 1的不对称1,6-共轭烯丙基化反应，具有良好的作用范围和高的对映选择性。
Catalytic asymmetric conjugate allylation of unsaturated carbonyl compounds is usually difficult to achieve, as 1,2-addition proceeds dominantly and high asymmetric induction is a challenging task. Herein, we disclose a copper(I)-NHC complex catalyzed asymmetric 1,6-conjugate allylation of 2,2-dimethyl-6-alkenyl-4H-1,3-dioxin-4-ones. The phenolic hydroxyl group in NHC ligands is found to be pivotal to obtain the desired products. Both aryl group and alkyl group at δ-position are well tolerated with the corresponding products generated in moderate to high yields and high enantioselectivity. Moreover, both 2-substituted and 3-substituted allylboronates serve as acceptable allylation reagents. At last, the synthetic utility of the products is demonstrated in several transformations by means of the versatile terminal olefin and dioxinone groups. Catalytic asymmetric conjugate allylation of unsaturated carbonyl compounds is usually difficult to achieve due to competing 1,2-addition. Here, the authors report a copper(I)-catalyzed asymmetric 1,6-conjugate allylation of 2,2-dimethyl-6-alkenyl-4H-1,3-dioxin-4-ones with good scope and high enantioselectivity.
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影响因子：
16.6
作者：
den Hartog, Tim;Harutyunyan, Syuzanna R.;Feringa, Ben L.
通讯作者：
Feringa, Ben L.
香豆素的催化不对称共轭烯丙基化
影响因子：
5.2
作者：
Kuang, Yulong;Liu, Xiaohua;Feng, Xiaoming
通讯作者：
Feng, Xiaoming
影响因子：
4.3
作者：
Blons, Charlie;Morin, Marie S. T.;Mauduit, Marc
通讯作者：
Mauduit, Marc
影响因子：
12.9
作者：
den Hartog, Tim;Huang, Yange;Feringa, Ben L.
通讯作者：
Feringa, Ben L.
影响因子：
4.9
作者：
Cui, Yi;Yamashita, Yasuhiro;Kobayashi, Shu
通讯作者：
Kobayashi, Shu