Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , Changchun, Jilin 130022, China.
J Am Chem Soc. 2015 Jan 21;137(2):632-5. doi: 10.1021/ja512029x. Epub 2015 Jan 12.
We present the enantioselective synthesis of P-stereogenic phosphinamides through Pd-catalyzed desymmetric ortho C-H arylation of diarylphosphinamides with boronic esters. The method represents the first example of the synthesis of P-stereogenic phosphorus compounds via the desymmetric C-H functionalization strategy. The reaction proceeded efficiently with a wide array of reaction partners to afford the P-stereogenic phosphinamides in up to 74% yield and 98% ee. The efficiency was further demonstrated by gram scale syntheses. Moreover, the flexible conversion of the P-stereogenic phosphinamides into various types of P-stereogenic phosphorus derivatives was also elaborated. Thus, the protocol provides a novel tool for the efficient and versatile synthesis of P-stereogenic compounds.
我们通过钯催化的二芳基膦酰胺与硼酸酯的不对称邻位 C-H 芳基化反应，展示了 P-手性膦酰胺的对映选择性合成。该方法代表了通过不对称 C-H 功能化策略合成 P-手性磷化合物的首例。该反应与广泛的反应伙伴高效进行，以高达 74%的产率和 98%的对映选择性提供 P-手性膦酰胺。通过克级合成进一步证明了该方法的效率。此外，还详细阐述了 P-手性膦酰胺灵活转化为各种类型的 P-手性磷衍生物。因此，该方案为高效、多功能的 P-手性化合物合成提供了一种新工具。
