Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave, Cambridge, MA 02139, USA.
Angew Chem Int Ed Engl. 2022 Nov 21;61(47):e202212630. doi: 10.1002/anie.202212630. Epub 2022 Oct 18.
α-Stereogenic allyl metalloids are versatile synthetic intermediates which can undergo various stereocontrolled transformations. Most existing methods to prepare α-stereogenic allyl metalloids involve multi-step sequences that curtail the number of compatible substrates and are limited to the synthesis of boronates. Here, we report a general method for the enantioselective preparation of α-stereogenic allyl metalloids utilizing dual CuH- and Pd-catalysis. This approach leverages a stereoretentive Cu-to-Pd transmetalation of an in situ generated alkyl copper species to allow access to enantioenriched allyl silanes, germanes, and boronate esters with broad functional group compatibility.
α-手性烯丙型类金属是多功能的合成中间体，可以经历各种立体控制的转化。大多数现有的制备α-手性烯丙型类金属的方法涉及多步序列，限制了相容底物的数量，并且仅限于硼酸酯的合成。在这里，我们报告了一种利用双 CuH 和 Pd 催化的对映选择性制备α-手性烯丙型类金属的通用方法。该方法利用立体保留的 Cu 到 Pd 的转移金属化作用，对原位生成的烷基铜物种进行，从而可以获得具有广泛官能团相容性的手性富集的烯丙基硅烷、锗烷和硼酸酯。
