Copper(I)-Catalyzed Regioselective Asymmetric Addition of 1,4-Pentadiene to Ketones
Copper(I)-Catalyzed Regioselective Asymmetric Addition of 1,4-Pentadiene to Ketones
复制标题
铜 (I) 催化 1,4-戊二烯与酮的区域选择性不对称加成
DOI：
10.1021/jacs.1c02084
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发表时间：
2021
影响因子：
15
通讯作者：
Liang Yin
中科院分区：
文献类型：
--
作者：
Feng Zhong;Zhi-Zhou Pan;Si-Wei Zhou;Hai-Jun Zhang;Liang Yin
通过使用市售的 1,4-戊二烯作为亲核试剂，实现了铜 (I) 催化的酮的区域选择性不对称烯丙基化。以高(Z)/(E)比和高对映选择性生成多种带有末端(Z)-1,3-二烯单元的手性叔醇。芳香族酮和脂肪族酮均可作为合适的底物。此外，与(E)-C1(烷基)-1,4-二烯的反应以中等产率进行，具有可接受的对映选择性，但(Z,E)/其他比例较低，这表明(E)-烯丙基铜(I)物质通过1,3-迁移部分异构化为(Z)-烯丙基铜(I)物质。随后的 Heck 反应和烯烃复分解反应弥补了 C1-1,4-二烯的低效率。该产品的合成效用通过铜(I)催化的1,3-二烯基团的区域选择性硼化得到进一步证明。
By using commercially available 1,4-pentadiene as a pronucleophile, a copper(I)-catalyzed regioselective asymmetric allylation of ketones is achieved. A variety of chiral tertiary alcohols bearing a terminal (Z)-1,3-diene unit are generated in high (Z)/(E) ratio and high enantioselectivity. Both aromatic ketones and aliphatic ketones serve as suitable substrates. Furthermore, the reactions with (E)-C1(alkyl)-1,4-dienes proceed in moderate yields with acceptable enantioselectivity but with low (Z,E)/others ratio, which demonstrates the partial isomerization of (E)-allylcopper(I) species to (Z)-allylcopper(I) species through 1,3-migration. Subsequent Heck reaction and olefin metathesis compensate for the low efficiency with C1-1,4-dienes. The synthetic utility of the product is further demonstrated by a copper(I)-catalyzed regioselective borylation of the 1,3-diene group.