Zhao Li-Ming, Gao Hua-Shuai, Li De-Feng, Dong Jing, Sang Lan-Lin, Ji Jie
School of Chemistry and Chemical Engineering, and Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou 221116, Jiangsu, China.
Org Biomol Chem. 2017 May 23;15(20):4359-4366. doi: 10.1039/c7ob00723j.
We report a simple, efficient, and general method for the zinc-mediated regioselective cinnamylation of aldehydes and ketones under Barbier-type conditions in a one-pot synthesis affording the corresponding α-cinnamylated alcohols in moderate to excellent yields. Compared to the literature procedures, this approach is operationally simple, uses simple reactants, and provides direct access to linear α-cinnamylated alcohols with excellent regioselectivity. Experimental results suggest that the reactions proceed through the radical pathway. In addition, the reaction was found to be scalable to the gram-scale and the one-pot protocol is also applicable to less reactive esters leading to bishomoallylic alcohols which were valuable intermediates for desymmetrizing intramolecular Heck cyclization, allowing for the elaboration to functionalized building blocks.
我们报道了一种简单、高效且通用的方法，即在巴比耶型条件下，通过锌介导醛和酮的区域选择性肉桂基化反应进行一锅合成，以中等至优异的产率得到相应的α-肉桂基化醇。与文献方法相比，该方法操作简单，使用简单的反应物，并能以优异的区域选择性直接得到线性α-肉桂基化醇。实验结果表明，反应通过自由基途径进行。此外，该反应可扩大至克级规模，且一锅法方案也适用于反应活性较低的酯，生成双高烯丙基醇，这些醇是分子内不对称Heck环化反应中用于去对称化的有价值中间体，可用于构建功能化结构单元。
