Amine-Tethered Phenylboronic Acid-Enabling Ring-Opening Strategy for Carbon Chain Elongation from Double Aldol Cyclic Hemiacetals
Amine-Tethered Phenylboronic Acid-Enabling Ring-Opening Strategy for Carbon Chain Elongation from Double Aldol Cyclic Hemiacetals
复制标题
胺系苯基硼酸使双羟醛环状半缩醛碳链伸长的开环策略
DOI：
10.1039/c9ob01263j
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Motomu Kanai
中科院分区：
文献类型：
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作者：
Yamato Kanzaki;Yuki Hirao;Harunobu Mitsunuma;Motomu Kanai
在环半缩醛形式的双醛上加入亲核碳试剂是合成结构吸引人的1,3-多元醇衍生物的一种很有前途的方法。然而，在中性条件下，环半缩醛通常对碳亲核试剂不起反应，因为亲电醛的功能被掩盖了。本文研制了一种胺系苯硼酸7g，可将双醛环半缩醛转化为开环线性醛。结合先前开发的铜催化不对称双醛醇反应(L. Lin， K. Yamamoto， H. Mitsunuma， Y. Kanzaki， S. Matsunaga和M. Kanai， J. Am。化学。Soc。， 2015, 137, 15418)，该方法产生了含有1,3-二醇或三醇片段的合成有用的手性构建块。
The addition of carbon nucleophiles to cyclic hemiacetal forms of double aldols is a promising approach toward the synthesis of structurally attractive 1,3-polyol derivatives. Cyclic hemiacetals are generally unreactive to carbon nucleophiles under neutral conditions, however, because the electrophilic aldehyde function is masked. Here we developed an amine-tethered phenylboronic acid 7g, which transforms double aldol cyclic hemiacetals to ring-opened linear aldehydes. Combined with the previously-developed copper-catalysed asymmetric double aldol reaction (L. Lin, K. Yamamoto, H. Mitsunuma, Y. Kanzaki, S. Matsunaga and M. Kanai, J. Am. Chem. Soc., 2015, 137, 15418), this method produced synthetically useful chiral building blocks containing a 1,3-di- or tri-ol moiety.